CN114751879B - Furanyl double-long-chain quaternary ammonium salt compound, preparation method and application thereof - Google Patents
Furanyl double-long-chain quaternary ammonium salt compound, preparation method and application thereof Download PDFInfo
- Publication number
- CN114751879B CN114751879B CN202210402607.7A CN202210402607A CN114751879B CN 114751879 B CN114751879 B CN 114751879B CN 202210402607 A CN202210402607 A CN 202210402607A CN 114751879 B CN114751879 B CN 114751879B
- Authority
- CN
- China
- Prior art keywords
- compound
- ammonium salt
- quaternary ammonium
- furyl
- double long
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
Abstract
The invention belongs to the technical field of disinfectants, and discloses a furyl double-long-chain quaternary ammonium salt compound, a preparation method and application thereof. The preparation method of the furyl double long-chain quaternary ammonium salt compound comprises the following steps: reacting a mixture containing a compound I and a compound ii in the presence of an alkaline or acidic substance to obtain the imine compound P; mixing the imine compound P with a reducing agent to react II, thus obtaining a double long chain secondary amine intermediate product K; or reacting the compound III in the presence of a halogenating agent to obtain the chloro compound O; mixing the chloro compound O with a compound i to react IV, so as to obtain a double long chain secondary amine intermediate product K; and (3) reacting the double long-chain secondary amine intermediate product K with a chloroethane reagent V to obtain the furyl double long-chain quaternary ammonium salt compound. The furyl double long chain quaternary ammonium salt compound of the invention has rapid killing effect on bacterial propagules as an organic disinfectant.
Description
Technical Field
The invention belongs to the technical field of disinfectants, and particularly relates to a furyl double-long-chain quaternary ammonium salt compound, a preparation method and application thereof as a disinfectant.
Background
To enhance personal daily health protection, reduce new coronavirus infection, developing efficient, safe, green disinfectant products is a common concern for society.
Compared with the traditional chlorine-containing disinfectants and peroxide disinfectants, the quaternary ammonium salt disinfectant has the advantages of low toxicity, small smell, convenient use, easy storage and the like, and is very suitable for being used as a household disinfection product.
Through the above analysis, the problems and defects existing in the prior art are as follows:
(1) The traditional disinfectant has strong irritation and can be used for a long time to damage human health;
(2) Traditional disinfectants have the disadvantage of poor biodegradability.
Disclosure of Invention
In order to overcome the problems in the related art, the disclosed embodiments of the invention provide a furyl double long chain quaternary ammonium salt compound, a preparation method and application thereof as a disinfectant.
The furyl double long chain quaternary ammonium salt compound as disinfectant has the following characteristics:
(1) The quaternary ammonium salt disinfectant has the characteristics of low toxicity, high efficiency, no stimulation and no corrosion;
(2) The quaternary ammonium salt disinfectant is prepared from small-molecule furan dicarboxaldehyde or furan dimethanol which are of a biological base platform, and has the advantages of wide raw material sources, environmental protection and reproducibility.
The technical scheme is as follows: a furyl double long chain quaternary ammonium salt compound is a compound with a structural formula shown in a formula I;
in one embodiment, the furyl double long chain quaternary ammonium salt compound comprises two quaternary ammonium salt substituents;
the substituent on the nitrogen atom of the quaternary ammonium salt group being a C 12 Alkyl long chain and two ethyl functional groups, and the anion is chloride.
The invention also aims to provide a preparation method of the furyl double long-chain quaternary ammonium salt compound, which comprises the following steps:
step 1, reacting a mixture containing a compound I and a compound ii in the presence of an alkaline substance or an acidic substance to obtain an imine compound P, wherein the structural formula of the imine compound P is shown as follows;
step 2, mixing the imine compound P with a reducing agent to perform a reaction II, so as to obtain a double-long-chain secondary amine intermediate product K, wherein the structural formula of the intermediate product K is shown as follows;
and step 3, reacting the double long chain secondary amine intermediate product K with a chloroethane reagent V to obtain the furyl double long chain quaternary ammonium salt compound.
In one embodiment, in step 1, the compound i is selected from compounds having the structural formula shown in formula III;
the compound ii is selected from compounds with a structural formula shown in a formula IV;
the alkaline substance is at least one selected from triethylamine and tributylamine; the acid substance is at least one selected from 0.5M-6M hydrochloric acid aqueous solution, 0.5M-6M acetic acid aqueous solution and p-toluenesulfonic acid;
in one embodiment, the conditions for reaction I in step 1 are: the reaction temperature is 30-100 ℃; the reaction time is 1 h-10 h;
the molar ratio of the compound i to the compound ii is 2-10:1-5;
in step 2, the reducing agent is at least one selected from sodium borohydride, sodium triethylborohydride, sodium cyanoborohydride, sodium triacetoxyborohydride and hydrogen;
in one embodiment, the conditions for reaction II in step 2 are: the reaction temperature is 0-100 ℃; the reaction time is 1 h-20 h;
the molar ratio of the imine compound P to the reducing agent is 1-5:1-10.
In one embodiment, the method for preparing the furyl double long chain quaternary ammonium salt compound comprises the following steps: in the presence of a solvent ether compound and an alkaline substance or an acidic substance, adding furan dicarboxaldehyde (3) and dodecanol (4), and reacting at 80 ℃ to prepare an imine compound (5); subsequently reducing the imine in the compound (5) by using a reducing agent to prepare a secondary amine compound (6); then, carrying out substitution reaction on the secondary amine compound (6) by utilizing chloroethane to prepare a target furyl double long-chain quaternary ammonium salt compound (1);
the preparation method of the furyl double long-chain quaternary ammonium salt compound has the following reaction formula:
the invention also aims to provide a preparation method of the furyl double long-chain quaternary ammonium salt compound, which comprises the following steps:
(A) Reacting compound III in the presence of a halogenating agent to give the chloro compound O;
the compound iii is selected from compounds with a structural formula shown in a formula V;
the structural formula of the compound O is as follows;
(B) Mixing the chloro compound O with a compound i to react IV, so as to obtain a double long chain secondary amine intermediate product K;
the compound i is selected from compounds with structural formulas shown in a formula III;
the structural formula of the double long chain secondary amine intermediate product K is as follows;
(C) And (3) reacting the double long-chain secondary amine intermediate product K with a chloroethane reagent V to obtain the furyl double long-chain quaternary ammonium salt compound.
In one embodiment, the method for preparing the furyl double long chain quaternary ammonium salt compound comprises the following steps:
in the presence of a solvent methylene dichloride, adding furan dimethanol (7) and a halogenated reagent (8), and reacting at 30 ℃ to prepare a dichloro compound (9); the secondary amine compound (6) is then prepared by substituting chlorine in the compound (9) with ethylenediamine (4). Then, carrying out substitution reaction on the secondary amine compound (6) by utilizing chloroethane to prepare a target furyl double long-chain quaternary ammonium salt compound (1);
the preparation method of the furyl double long-chain quaternary ammonium salt compound has the following reaction formula:
in one embodiment, the conditions for reaction III in step (a) are: the reaction temperature is 0-30 ℃; the reaction time is 1 to 5 hours;
the halogenated reagent is at least one selected from oxalyl chloride, thionyl chloride, phosphorus oxychloride, phosphorus tribromide and concentrated hydrochloric acid;
the molar ratio of the compound iii to the halogenated reagent is 1-5:2-10.
In one embodiment, the conditions for reaction IV in step (B) are: the reaction temperature is 30-100 ℃; the reaction time is 1 h-10 h;
the mol ratio of the chloro compound O to the chloro compound i is 1-5:2-10;
the conditions for reaction V in step (C) are: the reaction temperature is 30-100 ℃; the reaction time is 1 h-10 h.
The molar ratio of the double long chain secondary amine intermediate product K to the chloroethane reagent is 1-10:4-20.
The invention also aims to provide the application of the furyl double long-chain quaternary ammonium salt compound as a disinfectant.
By combining all the technical schemes, the invention has the advantages and positive effects that:
first, aiming at the technical problems in the prior art and the difficulty in solving the problems, the technical problems solved by the technical proposal of the invention are analyzed in detail and deeply by tightly combining the technical proposal to be protected, the results and data in the research and development process, and the like, and some technical effects brought after the problems are solved have creative technical effects. The specific description is as follows:
the invention develops a furyl double long-chain quaternary ammonium salt compound by taking a biological base platform compound furan dicarboxaldehyde or furan dicarboxalcohol as a raw material, and the compound has a more efficient killing effect on staphylococcus aureus compared with a single-chain quaternary ammonium salt disinfectant.
The furyl double long chain quaternary ammonium salt compound of the invention has rapid killing effect on bacterial propagules as an organic disinfectant. Through killing experiments on staphylococcus aureus, the furyl double long-chain quaternary ammonium salt disinfectant disclosed by the invention is compared with a single-chain quaternary ammonium salt disinfectant, and the furyl double long-chain quaternary ammonium salt disinfectant disclosed by the invention has a stronger bactericidal effect. After the disinfectant is prepared into 2g/L ethanol disinfectant, the disinfectant acts on staphylococcus aureus suspension, and after 30 seconds, the disinfectant has a killing logarithmic value of more than 5.00, and has a killing effect which is more than 2 times that of a single-chain quaternary ammonium salt disinfectant.
Secondly, the technical scheme is regarded as a whole or from the perspective of products, and the technical scheme to be protected has the following technical effects and advantages:
the furyl double long chain quaternary ammonium salt compound provided by the invention takes a biological base platform compound furan dicarboxaldehyde or furan dicarboxyl alcohol as a raw material, has a furan ring, double quaternary ammonium salt substituent groups and double long alkyl chains in the structure, can be used as a disinfectant, and can be converged on the surface of a thallus to influence the permeability of the thallus when the quaternary ammonium salt disinfectant contacts bacteria by constructing two quaternary ammonium salt functional groups and two alkyl long chains in the structure to serve as hydrophilic functional groups and hydrophobic functional groups respectively, so that moisture enters the thallus to cause swelling and cracking and kill the bacteria. Meanwhile, the disinfectant also has the functions of denaturing protein, affecting bacterial metabolism, inactivating dehydrogenase/oxidase in bacteria, decomposing enzyme systems such as glucose, and the like. These properties make the quaternary ammonium salt disinfectant show excellent antibacterial and bactericidal effects.
Thirdly, as inventive supplementary evidence of the claims of the present invention, the following important aspects are also presented:
(1) The production value of the disinfectant in China steadily increases in 2015-2019, and the annual acceleration rate reaches about 5.5%. Affected by epidemic situation, the annual growth rate in 2020 reaches 13.7%. In the latter epidemic age, disinfection protection articles are pushed to market high points, disinfection is not only a requirement for medical places and people-stream dense areas, and household disinfection requirements are becoming the immediate requirement for consumption in a medium and short period. The disinfectant industry is a traditional subdivision chemical industry, the product coverage crowd is more, the downstream demand of the product is extremely wide, and the disinfectant is not only a necessary product in the medical service industry, but also plays an indispensable role in daily life and production. The technical scheme of the invention can provide a disinfectant product which is high-efficiency, low-toxicity, non-irritating and non-corrosive, is very suitable for household disinfection and public facility disinfection, is beneficial to epidemic prevention and control, and can bring great commercial value.
(2) The raw materials for preparing the disinfectant are from the bio-based platform compound furan dicarboxaldehyde or furan dimethanol, the raw materials are wide in source, green and environment-friendly and renewable, and the disinfectant is an important attempt for replacing petroleum-based products by adopting bio-based products, has important significance for promoting China to accelerate the realization of 'carbon reaching peak and carbon neutralization' development targets, and meets the strategic requirements of sustainable development.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the disclosure and together with the description, serve to explain the principles of the disclosure.
FIG. 1 is a flow chart of a preparation method of furan-based double-long-chain quaternary ammonium salt disinfectant provided in the embodiment 1 of the invention;
FIG. 2 is a flow chart of a preparation method of the furyl double long-chain quaternary ammonium salt disinfectant provided in the embodiment 2 of the present invention;
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
1. Explanation of the examples:
the embodiment of the invention provides a preparation method of a furyl double long-chain quaternary ammonium salt compound, which comprises the following steps: and reacting the obtained double long chain secondary amine intermediate product K with a chloroethane reagent V to obtain the furyl double long chain quaternary ammonium salt compound.
The structural formula of the double long chain secondary amine intermediate product K is shown as follows;
example 1
The embodiment of the invention provides a furyl double long-chain quaternary ammonium salt compound, wherein the furyl double long-chain quaternary ammonium salt compound is selected from compounds with a structural formula shown in a formula I, and the compound is caramel viscous liquid and is easy to dissolve in water and alcohol solvents;
the structure of the compound contains two quaternary ammonium salt substituents.
The substituent on the nitrogen atom of the quaternary ammonium salt group is a C12 alkyl long chain and two ethyl functional groups, and the anion is chloride.
Example 2
Based on the furyl double long-chain quaternary ammonium salt compound provided in the embodiment 1 of the invention, as shown in fig. 1, the preparation method of the furyl double long-chain quaternary ammonium salt compound provided in the embodiment of the invention comprises the following steps:
s101, reacting a mixture containing a compound I and a compound ii in the presence of an alkaline substance or an acidic substance to obtain the imine compound P, wherein the structural formula of the imine compound P is shown as follows;
s102, mixing the imine compound P with a reducing agent to perform a reaction II, so as to obtain a double-long-chain secondary amine intermediate product K, wherein the structural formula of the intermediate product K is shown as follows;
s103, reacting the double long chain secondary amine intermediate product K with a chloroethane reagent V to obtain the furyl double long chain quaternary ammonium salt compound.
Example 3
Based on the furyl double long-chain quaternary ammonium salt compound provided in the embodiment 1 of the invention, as shown in fig. 2, the preparation method of the furyl double long-chain quaternary ammonium salt compound provided in the embodiment of the invention comprises the following steps:
s201, reacting a compound III in the presence of a halogenating agent to obtain the chloro compound O; the compound iii is selected from compounds with a structural formula shown in a formula V;
the structural formula of the compound O is as follows;
s202, mixing the chloro compound O with a compound i to react IV, so as to obtain a double long chain secondary amine intermediate product K;
the compound i is selected from compounds with structural formulas shown in a formula III;
the structural formula of the double long chain secondary amine intermediate product K is as follows;
s203, reacting the double long chain secondary amine intermediate product K with a chloroethane reagent V to obtain the furyl double long chain quaternary ammonium salt compound.
Example 4
According to the preparation method of the furyl double long-chain quaternary ammonium salt compound provided in the embodiment 2 of the present invention, as a preferred embodiment, in the step S101, the compound i is selected from compounds having a structural formula shown in formula III;
the compound ii is selected from compounds with a structural formula shown in a formula IV;
the alkaline substance is at least one selected from triethylamine and tributylamine; the acidic material is at least one selected from hydrochloric acid aqueous solution (0.5M-6M), acetic acid aqueous solution (0.5M-6M) and p-toluenesulfonic acid.
The reducing agent is at least one selected from sodium borohydride, sodium triethylborohydride, sodium cyanoborohydride, sodium triacetoxyborohydride and hydrogen.
The molar ratio of the compound i to the compound ii is 2-10:1-5.
The conditions of reaction I in step S101 are: the reaction temperature is 30-100 ℃; the reaction time is 1 h-10 h.
In the step S102, the molar ratio of the imine compound P to the reducing agent is 1-5:1-10.
The conditions of reaction II in step S102 are: the reaction temperature is 0-100 ℃; the reaction time is 1 h-20 h.
The conditions for reaction V in step S103 are: the reaction temperature is 30-100 ℃; the reaction time is 1 h-10 h.
Example 5
According to the preparation method of the furyl double long-chain quaternary ammonium salt compound provided by the embodiment 2, as a preferable embodiment, the furyl double long-chain quaternary ammonium salt compound can be prepared from furan dicarboxaldehyde (3) and dodecyl amine (4). First, furan dicarboxaldehyde (3) and dodecanol (4) are added thereto in the presence of a solvent ether compound and an alkaline or acidic substance, and reacted at 80℃to prepare an imine compound (5). The imine in the compound (5) is then reduced with a reducing agent to produce the secondary amine compound (6). And then carrying out substitution reaction on the secondary amine compound (6) by utilizing chloroethane to prepare the target furyl double long-chain quaternary ammonium salt compound (1).
Scheme 1: preparation route I of furan-based double long-chain quaternary ammonium salt compound organic disinfectant:
example 6
According to the preparation method of the furyl double long-chain quaternary ammonium salt compound provided by the embodiment 3, as a preferable embodiment, the furyl double long-chain quaternary ammonium salt compound can be prepared from furan dimethanol (7) and a halogenated reagent (8). First, furandimethanol (7) and a halogenating agent (8) were added thereto in the presence of methylene chloride as a solvent, and reacted at 30℃to prepare a dichloro compound (9). The secondary amine compound (6) is then prepared by substituting chlorine in the compound (9) with ethylenediamine (4). And then carrying out substitution reaction on the secondary amine compound (6) by utilizing chloroethane to prepare the target furyl double long-chain quaternary ammonium salt compound (1).
Scheme 2: preparation route II of furan-based double long-chain quaternary ammonium salt compound organic disinfectant:
example 7
According to the preparation method of the furyl double long chain quaternary ammonium salt compound provided in the embodiment 3 of the present invention, as a preferred embodiment, the condition of the reaction III in the step S201 is: the reaction temperature is 0-30 ℃; the reaction time is 1 h-5 h.
Optionally, the halogenated reagent is at least one selected from oxalyl chloride, thionyl chloride, phosphorus oxychloride, phosphorus tribromide and concentrated hydrochloric acid.
The molar ratio of the compound iii to the halogenated reagent is 1-5:2-10.
The conditions of reaction IV in step S202 are: the reaction temperature is 30-100 ℃; the reaction time is 1 h-10 h. The mol ratio of the chloro compound O to the compound i is 1-5:2-10.
Example 8
According to the preparation method of the furyl double long chain quaternary ammonium salt compound provided in the embodiment 3 of the present invention, as a preferred embodiment, the condition of the reaction V in the step S203 is: the reaction temperature is 30-100 ℃; the reaction time is 1 h-10 h.
Example 9
According to the preparation method of the furyl double long chain quaternary ammonium salt compound provided by the embodiment 3 of the invention, as a preferred embodiment, in the step S202, the molar ratio of the double long chain secondary amine intermediate product K to the chloroethane reagent is 1-10:4-20.
Example 10
Based on the preparation method of the furyl double long-chain quaternary ammonium salt compound provided by the embodiments 2-14, at least one of the furyl double long-chain quaternary ammonium salt compounds prepared by the preparation method is applied to being used as a disinfectant. The disinfectant is used for killing bacteria.
Example 11
The embodiment of the invention provides a preparation method of a single-chain quaternary ammonium salt disinfectant, which comprises the following steps:
preparing a single-chain quaternary ammonium salt disinfectant;
the synthesis steps are as follows:
the method comprises the following steps:
step one: to a mixed solution of furfural (100 mg,1 equivalent), dodecylamine (1 equivalent) in 1, 4-dioxane (2 mL) was added triethylamine (0.5 equivalent) dropwise at room temperature, followed by stirring at 80 ℃. After the reactant furfural disappeared, the reaction was quenched by dropwise adding a saturated ammonium chloride aqueous solution, then 100mL of ethyl acetate was added to the reaction system, the mixture was washed with saturated brine and extracted three times, the organic phase was collected, the aqueous phase was extracted twice with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate or anhydrous sodium sulfate, the drying agent was removed by filtration, and the organic phase was concentrated on a silica gel column with petroleum ether: ethyl acetate 10: 1-petroleum ether: ethyl acetate 5:1 gradient elution to obtain the purified imine intermediate.
Step two: to the compound obtained in step one (100 mg,1 eq) was added sodium borohydride (5 eq) and tetrahydrofuran/water mixed solvent (4:1, 3 ml) at room temperature to obtain a mixture, which was stirred at 70 ℃ for 5 hours, and the reaction was monitored every 1 hour time plate (with petroleum ether: ethyl acetate 3:1). After the reaction is finished, dropwise adding a saturated ammonium chloride aqueous solution into the reaction solution, slowly quenching the reaction, adding 50ml of dichloromethane into the system, washing the mixed system for three times by using saturated saline, combining organic solvents for three times, drying, filtering, concentrating an organic phase to obtain a secondary amine crude product, and directly using the secondary amine crude product in the next reaction.
Step three: acetonitrile solvent (2 mL) and chloroethane (2.2 equivalent) are added into the secondary amine crude product obtained in the step two, the reaction is carried out for 3 hours at 80 ℃, the reaction is monitored every 1.5 hours (the secondary amine raw material is monitored by petroleum ether: ethyl acetate 3:1, the single-chain quaternary ammonium salt product is monitored by DCM: meOH=5:1), after the reaction is finished, the reaction solution is concentrated by a rotary evaporator, 50mL of dichloromethane is added into the concentrated solution, the saturated saline is used for washing and extracting for three times, the organic phases of the three times are combined, and the drying, the filtering and the concentration are carried out. Subsequently on a silica gel column, dichloromethane: methanol 20:1 eluting to obtain a purified single-chain quaternary ammonium salt product.
The second method is as follows:
step one: using furfuryl alcohol as a raw material, methylene chloride (1 mL) was added to furfuryl alcohol (100 mg,1 eq) to obtain a mixed solution, and thionyl chloride (1.1 eq) was slowly added dropwise to the mixed solution, followed by stirring at room temperature for 0.5 hours. After the reaction is finished, dropwise adding saturated sodium bicarbonate aqueous solution into the reaction solution, slowly quenching the reaction until no bubbles are generated in the reaction solution, adding 50ml of dichloromethane into the system, washing the mixed system with the saturated sodium bicarbonate aqueous solution and saturated saline water for three times, combining organic solvents for three times, drying, filtering, concentrating the organic phase to obtain a crude chloro product, and directly using the crude chloro product in the next reaction.
Step two: acetonitrile solvent (2 mL) and laurylamine (1.1 equivalent) are added into the chloro compound crude product obtained in the previous step, after the chloro compound is completely converted into a long-chain secondary amine product by reaction for 3 hours at 80 ℃, chloroethane reagent (2.2 equivalent) is dropwise added into the reaction system, the reaction is continued, after the long-chain secondary amine intermediate product completely disappears, the reaction solution is concentrated by a rotary evaporator, 50mL of dichloromethane is added into the concentrated solution after the concentration, the saturated saline solution is used for washing and extraction for three times, and the organic phases of the three times are combined, dried, filtered and concentrated. Subsequently on a silica gel column, dichloromethane: methanol 20:1 eluting to obtain a purified target product.
The embodiment of the invention also provides a preparation method of the furyl double long-chain quaternary ammonium salt compound, which comprises the following steps:
the synthesis steps are as follows:
the method comprises the following steps:
step one: to a mixed solution of furan dicarboxaldehyde (100 mg,1 eq.) and dodecylamine (2.1 eq.) in 1, 4-dioxane (2 mL) was added triethylamine (0.5 eq.) dropwise at room temperature, followed by stirring at 80 ℃. After the disappearance of the reactant furandicarboxaldehyde, the reaction is quenched by dropwise adding a saturated ammonium chloride aqueous solution, 100mL of ethyl acetate is added into the reaction system, the mixture is washed and extracted three times with saturated saline, an organic phase is collected, an aqueous phase is extracted twice with ethyl acetate, the organic phases are combined, anhydrous magnesium sulfate or anhydrous sodium sulfate is added for drying, a drying agent is removed by filtration, the organic phase is concentrated, and petroleum ether is used for preparing the organic phase on a silica gel column: ethyl acetate 10: 1-petroleum ether: ethyl acetate 5: and 1, gradient elution to obtain the purified long-chain diimine intermediate product.
Step two: to the compound obtained in step one (100 mg,1 eq) was added sodium borohydride (8 eq) and tetrahydrofuran/water mixed solvent (4:1, 3 ml) at room temperature to obtain a mixture, which was stirred at 70 ℃ for 6 hours, and the reaction was monitored every 1 hour time plate (with petroleum ether: ethyl acetate 1:1). After the reaction is finished, dropwise adding a saturated ammonium chloride aqueous solution into the reaction solution, slowly quenching the reaction, adding 50ml of dichloromethane into the system, washing the mixed system for three times by using saturated saline, combining organic solvents for three times, drying, filtering, concentrating an organic phase to obtain a long-chain secondary amine crude product, and directly using the product for the next reaction.
Step three: acetonitrile solvent (2 mL) and chloroethane (4.2 equivalent) are added into the long-chain secondary amine crude product obtained in the step two, the reaction is carried out for 3 hours at 80 ℃, the reaction is monitored every 1.5 hours (the secondary amine raw material is monitored by petroleum ether: ethyl acetate 3:1, the long-chain bisquaternary ammonium salt product is monitored by DCM: meOH=5:1), after the reaction is finished, the reaction solution is concentrated by a rotary evaporator, 50mL of dichloromethane is added into the concentrated solution, the saturated saline is used for washing and extracting for three times, and the organic phases of the three times are combined, dried, filtered and concentrated. Subsequently on a silica gel column, dichloromethane: methanol 20:1 eluting to obtain a purified long-chain biquaternary ammonium salt product.
The second method is as follows:
step one: using furandimethanol as a raw material, methylene chloride (1 mL) was added to furandimethanol (100 mg,1 eq) to obtain a mixed solution, thionyl chloride (2.1 eq) was slowly added dropwise to the mixed solution, and the mixture was stirred at room temperature for 0.5 hours. After the reaction is finished, dropwise adding saturated sodium bicarbonate aqueous solution into the reaction solution, slowly quenching the reaction until no bubbles are generated in the reaction solution, adding 50ml of dichloromethane into the system, washing the mixed system with the saturated sodium bicarbonate aqueous solution and saturated saline water for three times, combining organic solvents for three times, drying, filtering, concentrating the organic phase to obtain a crude chloro product, and directly using the crude chloro product in the next reaction.
Step two: acetonitrile solvent (2 mL) and laurylamine (2.1 equivalent) are added into the chloro compound crude product obtained in the previous step, after the chloro compound is completely converted into a long-chain secondary amine product by reaction for 3 hours at 80 ℃, chloroethane reagent (4.2 equivalent) is dropwise added into the reaction system, the reaction is continued, after the long-chain secondary amine intermediate product completely disappears, the reaction solution is concentrated by a rotary evaporator, 50mL of dichloromethane is added into the concentrated solution after the concentration, the saturated saline solution is used for washing and extraction for three times, and the organic phases of the three times are combined, dried, filtered and concentrated. Subsequently on a silica gel column, dichloromethane: methanol 20:1 eluting to obtain a purified target product.
In the foregoing embodiments, the descriptions of the embodiments are emphasized, and in part, not described or illustrated in any particular embodiment, reference is made to the related descriptions of other embodiments.
2. Evidence of example related effects:
experiment
Evaluation of sterilizing Performance
Preparing 2g/L ethanol disinfectant from the furyl double long-chain quaternary ammonium salt compound and the single-chain quaternary ammonium salt compound in ethanol, and testing microorganism golden yellowStaphylococci (ATCC 6538) were purchased from China general microbiological culture collection center. And preparing staphylococcus aureus suspension according to 2.1.1.2.3 method in 2002 edition of disinfection technical Specification. The bacterial content of the suspension is 1 multiplied by 10 7 ～5×10 7 cfu/mL. The sterilization test is carried out at a water bath temperature of 20 ℃, and the bacterial suspension and the disinfectant solution are firstly subjected to constant temperature operation. Subsequently, 0.5mL of staphylococcus aureus suspension and 0.5mL of Bovine Serum Albumin (BSA) were added to the sterile tube, and 4mL of sterilizing solution at 1.25 times the experimental concentration was added thereto, mixed well and timed. Respectively acting for 30s and 60s, taking 0.5mL of bacterial sample liquid, adding the bacterial sample liquid into a 4.5mL neutralizer test tube, uniformly mixing the bacterial sample liquid and the neutralizer test tube, and neutralizing the bacterial sample liquid for 10 minutes. Subsequently, 1mL of the sample solution was taken out, the number of viable bacteria was measured by a viable bacteria culture counting method, and each tube of the bacterial sample solution was inoculated to 2 dishes. The samples were then placed in a 37℃incubator, the experimental results were observed after 48 hours, and the viable bacteria concentration (cfu/mL) of each group was calculated to obtain the killing log value. The above test was repeated 3 times in parallel. Wherein the proportion of the neutralizer is as follows: 30g/L saponin, 10g/L sodium thiosulfate, 20g/L lecithin and 30g/L Tween-80 TSB, the neutralization reagent can effectively neutralize the quaternary ammonium salt disinfectant.
From the experimental data, the furyl double long-chain quaternary ammonium salt compound provided by the invention has extremely strong sterilization effect on golden yellow grape balls as an organic disinfectant. Compared with the single-chain quaternary ammonium salt disinfectant, the bactericidal effect exceeds 2 times 1.
While the invention has been described with respect to what is presently considered to be the most practical and preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (7)
1. The furyl double long-chain quaternary ammonium salt compound is characterized in that the furyl double long-chain quaternary ammonium salt compound is a compound with a structural formula shown in a formula I;
2. a method for preparing the furyl double long-chain quaternary ammonium salt compound according to claim 1, which is characterized in that the method for preparing the furyl double long-chain quaternary ammonium salt compound comprises the following steps:
step 1, a mixture containing a compound I and a compound ii is reacted in the presence of an alkaline substance or an acidic substance to obtain an imine compound P, wherein the structural formula of the imine compound P is as follows:
step 2, mixing the imine compound P with a reducing agent to perform a reaction II, and obtaining a double long chain secondary amine intermediate product K, wherein the structural formula is as follows:
step 3, reacting the double long chain secondary amine intermediate product K with a chloroethane reagent V to obtain a furyl double long chain quaternary ammonium salt compound;
in step 1, the compound i is selected from compounds having a structural formula shown in formula III;
the compound ii is selected from compounds with a structural formula shown in a formula IV;
the alkaline substance is at least one selected from triethylamine and tributylamine;
the acid substance is at least one selected from 0.5M-6M hydrochloric acid aqueous solution, 0.5M-6M acetic acid aqueous solution and p-toluenesulfonic acid;
the molar ratio of the compound i to the compound ii is 2-10:1-5;
the conditions for reaction I were: the reaction temperature is 30-100 ℃ and the reaction time is 1-10 h;
in step 2, the reducing agent is at least one selected from sodium borohydride, sodium triethylborohydride, sodium cyanoborohydride, sodium triacetoxyborohydride and hydrogen;
the molar ratio of the imine compound P to the reducing agent is 1-5:1-10;
the conditions for reaction II were: the reaction temperature is 0-100 ℃, and the reaction time is 1-20 h.
3. The method for producing a furyl double long-chain quaternary ammonium salt compound according to claim 2, wherein the method for producing a furyl double long-chain quaternary ammonium salt compound comprises: in the presence of a solvent ether compound and an alkaline substance or an acidic substance, furan dicarboxaldehyde and dodecyl amine are added for reaction at 80 ℃ to prepare an imine compound; reducing the imine in the compound by using a reducing reagent to prepare a secondary amine compound; then, carrying out substitution reaction on the secondary amine compound by utilizing chloroethane to prepare the target furyl double long-chain quaternary ammonium salt compound;
the preparation method of the furyl double long-chain quaternary ammonium salt compound has the following reaction formula:
4. a method for preparing the furyl double long-chain quaternary ammonium salt compound according to claim 1, which is characterized in that the method for preparing the furyl double long-chain quaternary ammonium salt compound comprises the following steps:
(A) Reacting compound III in the presence of a halogenating agent to give the chloro compound O;
the compound iii is selected from compounds with a structural formula shown in a formula V;
the structural formula of the compound O is as follows;
(B) Mixing the chloro compound O with a compound i to react IV, so as to obtain a double long chain secondary amine intermediate product K;
the compound i is selected from compounds with structural formulas shown in a formula III;
the structural formula of the double long chain secondary amine intermediate product K is shown in the following figure;
(C) And (3) reacting the double long-chain secondary amine intermediate product K with a chloroethane reagent V to obtain the furyl double long-chain quaternary ammonium salt compound.
5. The method for producing a furyl double long-chain quaternary ammonium salt compound according to claim 4, wherein the method for producing a furyl double long-chain quaternary ammonium salt compound comprises:
in the presence of a solvent methylene dichloride, adding furandimethanol and a halogenated reagent, and reacting at 30 ℃ to prepare a dichloro compound; then, the chlorine in the compound is replaced by the dodecyl amine to prepare a secondary amine compound; then, carrying out substitution reaction on the secondary amine compound by utilizing chloroethane to prepare the target furyl double long-chain quaternary ammonium salt compound;
the preparation method of the furyl double long-chain quaternary ammonium salt compound has the following reaction formula:
6. the method for producing a furyl double long chain quaternary ammonium salt compound according to claim 4, wherein the conditions for reaction III in step (a) are: the reaction temperature is 0-30 ℃; the reaction time is 1 to 5 hours;
the halogenated reagent is at least one selected from oxalyl chloride, thionyl chloride, phosphorus oxychloride, phosphorus tribromide and concentrated hydrochloric acid;
the molar ratio of the compound iii to the halogenated reagent is 1-5:2-10.
7. The method for producing a furyl double long chain quaternary ammonium salt compound according to claim 4, wherein the conditions of reaction IV in step (B) are: the reaction temperature is 30-100 ℃; the reaction time is 1 h-10 h;
the mol ratio of the chloro compound O to the chloro compound i is 1-5:2-10;
the conditions for reaction V in step (C) are: the reaction temperature is 30-100 ℃; the reaction time is 1 h-10 h;
the molar ratio of the double long chain secondary amine intermediate product K to the chloroethane reagent is 1-10:4-20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210402607.7A CN114751879B (en) | 2022-04-18 | 2022-04-18 | Furanyl double-long-chain quaternary ammonium salt compound, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210402607.7A CN114751879B (en) | 2022-04-18 | 2022-04-18 | Furanyl double-long-chain quaternary ammonium salt compound, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114751879A CN114751879A (en) | 2022-07-15 |
| CN114751879B true CN114751879B (en) | 2023-06-23 |
Family
ID=82331681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210402607.7A Active CN114751879B (en) | 2022-04-18 | 2022-04-18 | Furanyl double-long-chain quaternary ammonium salt compound, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114751879B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2477931C (en) * | 2002-03-05 | 2011-02-01 | Josef Ehrenfreund | O-cyclopropyl-carboxanilides and their use as fungicides |
| CA2531732C (en) * | 2003-07-09 | 2012-04-10 | Paratek Pharmaceuticals, Inc. | Prodrugs of 9-aminomethyl tetracycline compounds |
| RU2017108785A (en) * | 2011-06-24 | 2019-01-22 | Доу Агросаенсиз Ллк | PESTICIDAL COMPOSITIONS AND RELATED WAYS |
| CN102503837A (en) * | 2011-10-17 | 2012-06-20 | 太原理工大学 | Tertiary amines and organic silicon quaternary ammonium salts containing double long chains and benzyl groups and preparation methods thereof |
| CN104262182A (en) * | 2014-08-22 | 2015-01-07 | 江苏万淇生物科技有限公司 | Novel bis(long-chain ester group) quaternary ammonium salts and synthetic process thereof |
-
2022
- 2022-04-18 CN CN202210402607.7A patent/CN114751879B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114751879A (en) | 2022-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Salama et al. | Synthesis, characterization and biological activity of Schiff bases based on chitosan and arylpyrazole moiety | |
| Kenawy et al. | Synthesis and antimicrobial activity of α-aminophosphonates containing chitosan moiety | |
| CN107805208A (en) | A kind of preparation method of reactable gemini quaternary ammonium salt Bactericides Used in Leather Industry | |
| CN105601638B (en) | A kind of chlorophyllin derivative and preparation method thereof, as the application of photosensitive bacteriostatic agent and light sensitive pesticides | |
| CN114751879B (en) | Furanyl double-long-chain quaternary ammonium salt compound, preparation method and application thereof | |
| CN113185422B (en) | Preparation method of tetraester-based gemini quaternary ammonium salt leather sterilization mildew inhibitor | |
| JPWO2019230543A1 (en) | Polymers with dipicorylamine structure, methods for producing them, antimicrobial agents and antibacterial methods | |
| Manolov et al. | Microwave-assisted synthesis of 1, 2, 3, 4-tetrahydroisoquinoline sulfonamide derivatives and their biological evaluation | |
| CN111349088B (en) | Indole-based heterocyclic compounds, preparation method thereof and application thereof in controlling plant diseases | |
| CS226412B2 (en) | Method of preparing paromomycin derivatives | |
| Yarkova | Chemical modification of humic acids by the introduction of indole-containing fragments | |
| Taniguchi et al. | Isolation of viridicatin from Penicillium crustosum, and physiological activity of viridicatin and its 3-carboxymethylene derivative on microorganisms and plants | |
| CN107624767A (en) | A kind of application of dipeptide compounds | |
| Shcherbakov et al. | Synthesis of N-Alkyl Enamino Ketones Based on 3-Acyl-4 H-polyfluorochromen-4-ones and Their Antimicrobial Activity | |
| CN116947790A (en) | Bio-based gemini quaternary ammonium salt and preparation method and application thereof | |
| Aparaschivei et al. | Sulfonic derivatives of 2-Mercaptobenzoxazole and its conjugates with poly (maleic anhydride-alt-vinyl acetate) with potential pharmacological applications | |
| CN104151371A (en) | N-acetylglucosamine-N'-acylamino thiourea as well as synthesis method and application thereof | |
| CN116903557B (en) | Composite sterilization mixture and preparation method thereof | |
| CN104788416A (en) | Novel flavonol natural product derivative, preparation method and application thereof | |
| CN111165504B (en) | Application of sesquiterpenoids and derivatives thereof in preparation of medicines for preventing and treating wheat scab | |
| CN116284026B (en) | Water-soluble cation molecular cage and synthetic method and application thereof | |
| JPH0959279A (en) | Water-soluble metal phthalocyanine derivative and deodorizing antimicrobial material containing the same | |
| CN116396497B (en) | Metal organic framework material, ligand structure thereof and application of metal organic framework material in nano enzyme | |
| CN109134444A (en) | The application of 3- (2- furans) -4 hydroxy coumarin class compound and preparation method thereof and plant epiphyte resisting | |
| CN102206191B (en) | 1, 4-bis (4-amino-5-mercapto-1, 2, 4-triazole)-benzene, its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |