阅读说明：本技术 含天然萜烯结构Gemini型季铵盐表面活性剂及其合成方法与应用 (Gemini type quaternary ammonium salt surfactant containing natural terpene structure, and synthetic method and application thereof ) 是由 蓝虹云 黄道战 霍尚朝 莫君明 于 2020-08-11 设计创作，主要内容包括：本发明属于林产精细化学品合成技术领域,具体公开了一种含天然萜烯结构Gemini型季铵盐表面活性剂及其合成方法与应用。该类表面活性剂兼有天然萜烯结构和烯丙基季铵功能基,并且具有如式(Ⅰ)所示结构,<Image he="117" wi="209" file="984462DEST_PATH_IMAGE001.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>,其中R<Sup>1</Sup>为疏水基团,是含天然萜烯结构的烯丙基；R<Sup>2</Sup>是桥联基团,为亚乙基、1,3-亚丙基或1,4-亚丁基；X为氯或溴。本发明含天然萜烯结构Gemini型季铵盐表面活性剂的合成方法是以含天然萜烯结构的烯丙基卤化物和二元叔胺为原料,通过季铵化反应制备得到目标产物。该表面活性剂具有较强的表面活性,良好的亲水性和抑菌活性,能够抑制细菌、真菌以及藻类的生长,可用作杀菌剂和灭藻剂。(The invention belongs to the technical field of forest fine chemical synthesis, and particularly discloses a Gemini type quaternary ammonium salt surfactant containing a natural terpene structure, and a synthesis method and application thereof. The surfactant has both a natural terpene structure and an allyl quaternary ammonium functional group and has a structure shown as a formula (I), wherein R is 1 Is hydrophobic group and is allyl containing natural terpene structure; r 2 Is a bridging group which is ethylene, 1, 3-propylene or 1, 4-butylene; x is chlorine or bromine. The invention relates to a method for synthesizing a Gemini type quaternary ammonium salt surfactant containing a natural terpene structure, which takes allyl halide containing a natural terpene structure and dibasic tertiary amine as raw materials and prepares a target product through quaternization reaction. The surfactant has strong surface activity, good hydrophilicity and bacteriostatic activity, can inhibit the growth of bacteria, fungi and algae, and can be used as bactericide and algicide.)

1. A Gemini type quaternary ammonium salt surfactant containing a natural terpene structure is characterized in that the surfactant has both a natural terpene structure and an allyl quaternary ammonium functional group in a molecular structure and has a structure shown in a formula (I),

wherein R is¹Is hydrophobic group and is allyl containing natural terpene structure; r²Is a bridging group which is ethylene, 1, 3-propylene or 1, 4-propyleneA butyl group; x is chlorine or bromine.

2. The application of the Gemini type quaternary ammonium salt surfactant containing the natural terpene structure according to claim 1 in serving as raw materials or products of surfactants, bacteriostats and bactericides.

3. A method for synthesizing the Gemini type quaternary ammonium salt surfactant containing the natural terpene structure according to any one of claims 1 to 2, which is characterized by comprising the following steps: according to the mass ratio of 2-2.1: 1, adding the allyl halide containing the natural terpene structure and the dibasic tertiary amine into a reactor, adding an organic solvent with the mass of 0-3 times that of the raw materials, heating, refluxing, stirring and reacting at 60-90 ℃ for 2-6 h, cooling to room temperature, adding a proper amount of the organic solvent, fully stirring, standing to precipitate a product, filtering and collecting the precipitate, purifying, and drying in vacuum to obtain the product.

4. The method for synthesizing the Gemini type quaternary ammonium salt surfactant containing the natural terpene structures as claimed in claim 3, wherein the allyl halide containing the natural terpene structures comprisesω-chloromethyl camphene (1),ω-chloromethyl longifolene (2),ωBromomethyl camphene (3) andωbromomethyl longifolene (4), the corresponding molecular structure of which is shown below:

。

5. the method for synthesizing the Gemini type quaternary ammonium salt surfactant containing the natural terpene structure as claimed in claim 3, wherein the dibasic tertiary amine comprises tetramethylethylenediamine, N, N-tetramethyl-1, 3-propanediamine and N, N, N, N-tetramethyl-1, 4-butanediamine.

6. The method for synthesizing the Gemini type quaternary ammonium salt surfactant containing the natural terpene structure as claimed in claim 3, wherein the organic solvent is one or a mixture of two or more of ethyl acetate, butyl acetate and acetone.

Technical Field

The invention belongs to the technical field of forest fine chemical synthesis, and particularly relates to a Gemini type quaternary ammonium salt surfactant containing a natural terpene structure, and a synthesis method and application thereof.

Background

The natural terpenes such as alpha-pinene, beta-pinene, camphene, longifolene and the like exist in a plurality of natural plant essential oils, are also important turpentine products, have certain biological activities such as inflammation diminishing, pain easing, antibiosis or anticancer and the like, and have important application and development prospects in the fields of medicines, pesticides and the like. However, due to their volatile and weak hydrophilic characteristics, it is difficult to directly apply them to hydrophilic systems or environments to exert their intended drug effects. Therefore, people use the chemical properties of the terpene derivatives to modify or derivatize molecular structures, introduce and construct functional groups for enhancing hydrophilicity and bioactivity, develop new products of natural terpene derivatives and widen new application fields.

Taking camphene and longifolene as examples, can be respectively prepared by Prins olefine aldehyde condensation reactionω-acetoxymethyl camphene andω-acetoxymethyl longifolene, and then respectively synthesizing through hydrolysis, halogenation reaction or one-step halogenation reactionω-hydroxymethylcamphene,ω-hydroxymethyl longifolene,ω-chloromethyl camphene andωchloromethyl longifolene (blue rainbow cloud, et al. Fine chemical, 2018, 35 (7): 1255-1260; Huosheng, et al. Biochemical engineering, 2020, 54(7): 31-36)); the molecular structures of the camphene and the longifolene derivatives contain the molecular structures of natural camphene and longifolene, wherein,ω-chloromethyl camphene andωchloromethyl longifolenes are ascribed to allyl halides and have reactive chemical properties, e.g.ωThe chloromethyl longifolene and organic tertiary amine can be subjected to quaternization reaction to prepare a single-quaternary ammonium salt compound containing a longifolene structure,ω-chloromethyl camphene,ωChloromethyl longifolene and quaternary ammonium salt compound containing longifolene structure have specific structure to longifolene,ω-acetoxymethyl longifolene,ωHigher bacteriostatic activity of hydroxymethyl longifolene. The method has theoretical and practical application and research values for researching the relationship between the physical and chemical properties and the biological activity of the natural terpene structure and the derivative containing the natural terpene structure. However, the derivatives containing natural terpene structures are not abundant in variety and quantity, and especially the research on biological activity and application performance is not deep enough, so that the further popularization and application of the derivatives are limited.

Disclosure of Invention

The invention aims to solve the problems existing in the conventional research and development of derivatives containing natural terpene structures, and provides a Gemini type quaternary ammonium salt surfactant containing natural terpene structures, a synthetic method and application thereof, namely an active methylene splicing principle designed based on drug synthesis so as to solve the problemsω-chloromethyl camphene andωthe method comprises the steps of taking allyl halide containing a natural terpene structure such as chloromethyl longifolene and the like as a raw material, adopting a one-step or two-step quaternization reaction process to construct a quaternary ammonium functional group with hydrophilicity, antibacterial activity and algae inhibiting activity, synthesizing a Gemini type quaternary ammonium salt surfactant with the natural terpene structure and the allyl quaternary ammonium functional group, and providing the application of the surfactant in the aspects of raw materials or products as a surfactant, a bacteriostatic agent and a bactericide.

In order to achieve the purpose, the invention adopts the following technical scheme:

a Gemini type quaternary ammonium salt surfactant containing a natural terpene structure has a molecular structure which has both a natural terpene structure and an allyl quaternary ammonium functional group and has a structure shown in a formula (I),

wherein R is¹Is hydrophobic group and is allyl containing natural terpene structure; r²Is a bridging group which is ethylene, 1, 3-propylene or 1, 4-butylene; x is chlorine or bromine. The knot containing natural terpeneThe constitutional allyl group is derived from an allyl halide containing a natural terpene structure.

The invention also provides application of the Gemini type quaternary ammonium salt surfactant containing the natural terpene structure in the aspects of being used as raw materials or products of surfactants, bacteriostats and bactericides.

The invention also provides a synthetic method of the Gemini type quaternary ammonium salt surfactant containing the natural terpene structure, which comprises the following steps: according to the mass ratio of 2-2.1: 1, adding the allyl halide containing the natural terpene structure and the dibasic tertiary amine into a reactor, adding an organic solvent with the mass of 0-3 times that of the raw materials, heating, refluxing, stirring and reacting at 60-90 ℃ for 2-6 h, cooling to room temperature, adding a proper amount of the organic solvent, fully stirring, standing to precipitate a product, filtering and collecting the precipitate, purifying, and drying in vacuum to obtain the product.

In the method for synthesizing the Gemini type quaternary ammonium salt surfactant containing the natural terpene structure, the allyl halide containing the natural terpene structure comprisesω-chloromethyl camphene (1),ω-chloromethyl longifolene (2),ωBromomethyl camphene (3) andωbromomethyl longifolene (4), the corresponding molecular structure of which is shown below:

the allyl halide containing the natural terpene structure is prepared by taking natural terpenes such as camphene, longifolene and the like as raw materials through Prins olefine aldehyde condensation, hydrolysis, halogenation and other reactions according to the methods in the documents [ Nayak U.R., et al Tetrahedron, 1963, 19(12): 2281-2292; Huoshangchao, et al biomass chemical engineering, 2020, 54(3): 31-36; Yaoda Shu synthetic chemistry, 1998, (3): 315-318; Snyder E.J. org. chem., 1972, 37, 212 ]; the natural terpenes comprise monoterpenes such as camphene, beta-pinene and alpha-pinene and sesquiterpenes such as longifolene.

In the method for synthesizing the Gemini type quaternary ammonium salt surfactant containing the natural terpene structure, the dibasic tertiary amine comprises tetramethylethylenediamine, N, N-tetramethyl-1, 3-propanediamine and N, N, N, N-tetramethyl-1, 4-butanediamine.

In the synthesis method of the Gemini type quaternary ammonium salt surfactant containing the natural terpene structure, the organic solvent is any one or a mixture of two or more of ethyl acetate, butyl acetate and acetone.

The Gemini type quaternary ammonium salt surfactant containing the natural terpene structure provided by the invention has both the natural terpene structure and the allyl quaternary ammonium functional group, shows stronger surface activity, can inhibit the growth of bacteria, fungi and algae, and can be used as a raw material or a product of the surfactant, the bacteriostatic agent and the algicide.

The Gemini quaternary ammonium salt surfactant containing the natural terpene structure is synthesized according to the synthesis method of the Gemini quaternary ammonium salt surfactant containing the natural terpene structure, wherein the molecular structure of the synthesized Gemini quaternary ammonium salt surfactant part containing the natural terpene structure Ia-Id is as follows:

the names of the Gemini type quaternary ammonium salt surfactants Ia-Id containing the natural terpene structures are respectively as follows: ia, N₁,N₂-bis (camphenylmethyl) -N₁,N₁,N₂,N₂-tetramethylethane-1, 2-ammonium dichloride; ib, N₁,N₂-bis (longifolenylmethyl) -N₁,N₁,N₂,N₂-tetramethylethane-1, 2-ammonium dichloride; ic, N₁,N₃-bis (camphenylmethyl) -N₁,N₁,N₃,N₃-tetramethylpropane-1, 3-ammonium dichloride; id, N₁,N₄-bis (longifolenylmethyl) -N₁,N₁,N₄,N₄-tetramethylbutane-1, 2-dibromide.

The molecular structure of the Gemini type quaternary ammonium salt surfactant containing the natural terpene structure obtained by the synthesis of the invention is subjected to infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy (F)¹H-NMR and¹³C-NMR), the apparatus and method used were as follows: magna IR550 (ii) type fourier transform infrared spectroscopy (FT-IR) instrument, Nicolet corporation, usa; 600M Nuclear magnetic resonance Spectroscopy (NMR) apparatus (CDCl)₃As solvent, internal standard TMS), japan electronics corp.

The surface activity of the Gemini type quaternary ammonium salt surfactant containing a natural terpene structure is expressed by the surface tension to water, and is measured by a hanging ring method; the emulsifying property is measured by a water diversion method; the bacteriostatic and bactericidal activity evaluation adopts a two-fold dilution method of 96-well plate trace broth.

Compared with the prior art, the invention has the following advantages:

(1) the Gemini type quaternary ammonium salt surfactant containing the natural terpene structure provided by the invention has good hydrophilicity, surface activity and bacteriostatic activity, can inhibit the growth of common pathogenic bacteria (escherichia coli, klebsiella pneumoniae, staphylococcus aureus, bacillus subtilis and the like), fungi (candida albicans, candida tropicalis, aspergillus niger and the like) and algae (freshwater algae and marine algae), and can be used as an antibacterial agent or an algistat.

(2) The invention provides a novel Gemini type quaternary ammonium salt surfactant product containing a natural terpene structure, which contains a molecular structure of natural terpene, can be used as a botanical antibacterial or algae inhibitor and has good application prospect.

Drawings

FIG. 1 shows N synthesized in example 1 of the present invention₁,N₂-bis (camphenylmethyl) -N₁,N₁,N₂,N₂-graph of infrared spectrum (FT-IR) of tetramethylethane-1, 2-ammonium dichloride (Ia);

FIG. 2 shows N synthesized in example 1 of the present invention₁,N₂-bis (camphenylmethyl) -N₁,N₁,N₂,N₂Process for preparing (Ia) tetramethylethane-1, 2-ammonium dichloride¹H nuclear magnetic resonance spectrum (¹H-NMR) chart;

FIG. 3 shows N synthesized in example 1 of the present invention₁,N₂-bis (camphenylmethyl) -N₁,N₁,N₂,N₂Process for preparing (Ia) tetramethylethane-1, 2-ammonium dichloride¹³C nuclear magnetic resonance spectrum (¹³C-NMR).

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.