CN114456183A - Clathrate compound of anion ring-opening cucurbituril and vanillin spice and preparation method and application thereof - Google Patents

Clathrate compound of anion ring-opening cucurbituril and vanillin spice and preparation method and application thereof Download PDF

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CN114456183A
CN114456183A CN202210121773.XA CN202210121773A CN114456183A CN 114456183 A CN114456183 A CN 114456183A CN 202210121773 A CN202210121773 A CN 202210121773A CN 114456183 A CN114456183 A CN 114456183A
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vanillin
cucurbituril
anion
opening
ring
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殷沛沛
杨波
王保兴
张舒清
卢伟
周桂园
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China Tobacco Yunnan Industrial Co Ltd
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China Tobacco Yunnan Industrial Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/10—Natural spices, flavouring agents or condiments; Extracts thereof
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
    • A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
    • A24B15/301—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances by aromatic compounds
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
    • A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
    • A24B15/36—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring
    • A24B15/38—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring having only nitrogen as hetero atom
    • A24B15/385—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring having only nitrogen as hetero atom in a five-membered ring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
    • C07C47/575—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0061—Essential oils; Perfumes compounds containing a six-membered aromatic ring not condensed with another ring
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Abstract

The invention discloses an inclusion compound of an anion ring-opening cucurbituril and a vanillin spice and a preparation method and application thereof. The preparation method comprises the following steps: adding the anion ring-opening cucurbituril solid powder into a reaction kettle, adding a proper amount of pure water, and heating and stirring to completely dissolve the anion ring-opening cucurbituril solid powder; stopping heating after dissolving, cooling the solution to room temperature, directly adding vanillin perfume or dissolving vanillin perfume in organic solvent, adding into water solution of anion ring-opening cucurbituril, and stirring; filtering, and drying the filtrate to obtain the target product of the clathrate compound of the anion ring-opening cucurbituril and the vanillin spice. The anion ring-opening cucurbituril and vanillin spice inclusion compound prepared by the invention can obviously improve the thermal stability of vanillin spices, can be applied to the fields of essence spices, tobacco, cosmetics, food, nutritional health-care products and the like, can realize the slow release and controlled release of vanillin spices, and is more stable and safe.

Description

Clathrate compound of anion ring-opening cucurbituril and vanillin spice and preparation method and application thereof
Technical Field
The invention relates to the technical field of essence and spice, tobacco, cosmetics, food and nutritional health care products, in particular to a clathrate compound of anion ring-opening cucurbituril and vanillin spice and a preparation method and application thereof.
Background
Vanillin (vanillin), also known as vanillin, has a chemical name of 3-methoxy-4-hydroxybenzaldehyde, has a strong milk flavor, and is a broad-spectrum type spice. It is not only in natural vanilla and other plants, but also can be artificially synthesized, and is the most widely used spice in the world. The application is very wide: in the food field, the milk flavor enhancer is widely used in various flavor blended foods needing to increase milk flavor, such as ice cream, chocolate, candy, cake and the like, and can also be added into infant formula foods; in the aspect of daily chemicals, the deodorant can be used for deodorizing plastics, rubber and other industrial products; in the cosmetic industry, can be used as a fragrance raw material for perfumes, perfumed soaps, hand sanitizers, face creams and hand creams; in the chemical industry, as defoamers, vulcanizing agents and chemical precursors; also can be applied to analysis and detection. In addition, the unique bean flavor and milk flavor of vanillin make it widely used as a flavoring agent and a fixative for cigarettes. When the vanillin is used as an aromatizer, the stability of the vanillin is always concerned, and the process of increasing the stability and the water solubility of the vanillin can better exert the aroma of the vanillin, prolong the shelf life of essence, spice, tobacco, cosmetics, food and nutritional health care products and prevent the vanillin or other effective components in ingredients from being decomposed and damaged.
Cucurbiturils are cyclic oligomers formed by multiple glycoluril monomers linked by methylene bridges. The two ends of the upper opening and the lower opening have the same size, and the structure of the pumpkin is similar to that of a pumpkin, so that the cucurbituril is obtained. The binding of cucurbituril and guest molecule is mainly dependent on hydrogen bond, van der waals force, hydrophobic interaction and ion-dipole interaction, and the binding constant of the cucurbituril and the guest molecule can reach 1015M-1Much higher than cyclodextrin. Although cucurbiturils have a relatively rigid structure and good stability, most cucurbiturils have limited their use due to poor water solubility. In recent years, the ring-opened cucurbituril is a novel cucurbituril homolog composed of a glycoluril tetramer unit and two end-substituted aromatic rings as a rapidly-developed novel supramolecular host molecule. The ring-opening cucurbituril is provided with a flexible C-shaped cavity, and the size of the cavity can be properly adjusted, so that more guest molecules with different molecular weights can be accommodated, and the binding capacity of the ring-opening cucurbituril is enhanced; meanwhile, the two aromatic ring side walls can promote the pi-pi interaction between the host and the guest. In addition, the ring-opened cucurbituril has high solubility and ionic function due to solubilizing groups derived from the ends of two aromatic rings of the ring-opened cucurbituril, and the conditions are provided for the ring-opened cucurbituril to become an excellent carrier.
Therefore, the anion ring-opening cucurbituril can be used for carrying out inclusion reaction with the vanillin spice to prepare the inclusion compound, so that the stability of the vanillin spice is enhanced, and the sustained release performance and the sustained release practical application value of the vanillin spice are realized.
Disclosure of Invention
The invention aims to solve the technical problem of providing an inclusion compound of anion ring-opening cucurbituril and vanillin spice as well as a preparation method and application thereof.
The technical problem to be solved by the invention is realized by the following technical scheme:
an inclusion compound of anion ring-opening cucurbituril and vanillin spice, wherein the inclusion compound is formed by the reaction of vanillin spice and anion ring-opening cucurbituril, and the structural formula of the inclusion compound is one of the following six types:
Figure BDA0003498547980000031
preferably, in the above technical solution, the anion ring-opening cucurbituril is selected from one of the following compounds:
Figure BDA0003498547980000032
Figure BDA0003498547980000041
wherein R is ═ CH2)nSO3A, wherein A is Na or H, and n is 1-8.
Preferably, in the above technical solution, the chain length of the substituent group of the anion ring-opening cucurbituril is n ═ 2 and 3, i.e. R ═ (CH ═ 2 and 32)2SO3A and R ═ CH2)3SO3A。
Preferably, in the above technical solution, the vanillin spice is vanillin or vanillin.
A preparation method of an inclusion compound of anion ring-opening cucurbituril and vanillin spice comprises the following steps:
(1) adding the anion ring-opening cucurbituril solid powder into a reaction kettle, adding a proper amount of pure water, heating, and stirring for 30-60 min to completely dissolve the anion ring-opening cucurbituril solid powder;
(2) stopping heating after dissolution, cooling the solution to room temperature, directly adding vanillin spices or dissolving vanillin spices in an organic solvent, adding the solution into an aqueous solution of an anion ring-opening cucurbituril, and violently stirring and reacting at 0-90 ℃ for 1-192 hours;
(3) filtering to remove insoluble substances, and drying the filtrate to obtain the target product of the clathrate of the anion ring-opening cucurbituril and the vanillin spice.
Preferably, in the technical scheme, the heating temperature of the anion ring-opening cucurbituril in the step (1) is 30-100 ℃.
Preferably, in the technical scheme, the molar ratio of the anion ring-opening cucurbituril to the vanillin spice in the step (2) is 1 (1-10); the organic solvent is one or more of methanol, ethanol, petroleum ether, ethyl acetate, dimethyl sulfoxide, N-dimethylformamide, dichloromethane, tetrahydrofuran or acetone.
Preferably, in the above technical solution, the organic solvent is ethanol, dimethyl sulfoxide, N-dimethylformamide and tetrahydrofuran.
Preferably, in the above technical solution, the drying manner in step (3) is freeze drying, concentration drying under reduced pressure or spray drying.
An application of the clathrate of anion ring-opening cucurbituril and vanillin spice in preparing essence and spice, tobacco, cosmetics, food or nutritional health product is provided.
The technical scheme of the invention has the following beneficial effects:
the preparation method of the clathrate compound of the anion ring-opening cucurbituril and the vanillin spice is simple, convenient, safe and efficient to operate and control, and the synthesized product has high purity and excellent quality.
According to the invention, the flexible C-shaped cavity of the anion ring-opening cucurbituril molecule is utilized, and the size of the cavity is matched and can be included with vanillin substances, so that the vanillin perfume is endowed with controllable release performance through the inclusion effect of the anion ring-opening cucurbituril.
The invention improves the controllable release performance of the vanillin spices through the inclusion effect of the anion ring-opening cucurbituril, so that the vanillin spices have wider application prospect.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention.
FIG. 1 shows an anion ring-opened cucurbituril a (R ═ CH2)nSO3A, a ═ H, n ═ 3) nuclear magnetic resonance hydrogen spectra of the complex with ethyl vanillin, where: (a) ring-opened cucurbituril a (R ═ CH)2)nSO3A, a ═ H, n ═ 3); (b) ring-opened cucurbituril a (R ═ CH)2)nSO3A, a ═ H, n ═ 3) with ethyl vanillin; (c) ethyl vanillin.
FIG. 2 shows an anion ring-opened cucurbituril a (R ═ CH2)nSO3A, a ═ H, n ═ 3) and ethyl vanillin clathrate.
FIG. 3 shows an anion ring-opened cucurbituril a (R ═ CH2)nSO3A, a ═ H, n ═ 1) and vanillin clathrate X-ray diffraction spectrum contrast plots, in which: (a) ring-opened cucurbituril a (R ═ CH)2)nSO3A, a ═ H, n ═ 1); (b) ring-opened cucurbituril a (R ═ CH)2)nSO3A, a ═ H, n ═ 1) with vanillin; (c) vanillin is prepared.
FIG. 4 shows an anion ring-opened cucurbituril a (R ═ CH2)nSO3A, a ═ Na, n ═ 3) and ethylvanillin clathrate at different temperatures.
FIG. 5 shows an anion ring-opened cucurbituril a (R ═ CH2)nSO3Thermogravimetric (TGA) analysis of a, a ═ H, n ═ 4) with vanillin clathrates, where: (a) anion ring-opened cucurbituril a (R ═ CH2)nSO3A, a ═ H, n ═ 4) with vanillin; (b) anion ring-opened cucurbituril a (R ═ CH2)nSO3A physical mixture of a, a ═ H, n ═ 4) with vanillin; (c) anion ring-opened cucurbituril a (R ═ CH2)nSO3A, a ═ H, n ═ 4); (d) vanillin is prepared.
FIG. 6 shows an anion ring-opened cucurbituril b (R ═ CH2)nSO3A, a ═ H, n ═ 3) and the nmr hydrogen spectra of the ethyl vanillin clathrate compound, where: (a) anion ring opening cucurbituril b (R ═ CH2)nSO3A, a ═ H, n ═ 3); b) anion ring opening cucurbituril b (R ═ CH2)nSO3A, a ═ H, n ═ 3) with ethyl vanillin; c) ethyl vanillin.
FIG. 7 shows an anion ring-opened cucurbituril b (R ═ CH)2)nSO3A, A ═ Na, n ═ 8) and ethyl vanillin clathrateA spectral contrast analysis plot, wherein: (a) anion ring opening cucurbituril b (R ═ CH2)nSO3A, a ═ Na, n ═ 8) and ethyl vanillin; (b) anion ring opening cucurbituril b (R ═ CH2)nSO3A, a ═ Na, n ═ 8) and ethyl vanillin; (c) ethyl vanillin; (d) anion ring opening cucurbituril b (R ═ CH2)nSO3A,A＝Na,n＝8)。
Fig. 8 shows an anion ring-opened cucurbituril c (R ═ (CH)2)nSO3A, a ═ Na, n ═ 6) heat release profiles at different temperatures with the inclusion complex of vanillin.
Fig. 9 shows an anion ring-opened cucurbituril c (R ═ (CH)2)nSO3Thermogravimetric (TGA) analysis of a, a ═ Na, n ═ 5) with vanillin inclusion compounds, where: (a) anion ring opening cucurbituril c (R ═ CH2)nSO3A, a ═ Na, n ═ 5) and vanillin; (b) anion ring opening cucurbituril c (R ═ CH2)nSO3A, a ═ Na, n ═ 5) and vanillin; (c) anion ring opening cucurbituril c (R ═ CH2)nSO3A, a ═ Na, n ═ 5); (d) vanillin is prepared.
Detailed Description
Various exemplary embodiments of the present invention will now be described in detail with reference to the accompanying drawings. It should be noted that: the relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise.
Example 1
1.453g (1mmol) of anion ring-opened cucurbituril a (R ═ CH2)nSO3Dissolving solid powder of A, A ═ H, n ═ 3) in 15ml, heating at 30 deg.C and stirring for 30min to dissolve completely, stopping heating, allowing the solution to cool to room temperature, and adding 0.332g (2mmol) of ethyl vanillin directly to anion ring-opened cucurbituril a (R ═ CH ═ 2mmol)2)nSO3Stirring A, A ═ H, n ═ 3) in water solution at 25 deg.C for 48H, filtering to remove insoluble matter, freeze drying filtrate to obtain anion ring-opened cucurbituril a (R ═ CH (CH)2)nSO3A, a ═ H, n ═ 3) and ethyl joss-stickThe yield of the target product of the Lanxin clathrate compound is 98%.
As shown in fig. 1, the nmr hydrogen spectrum of the inclusion compound in this example: (a) ring-opened cucurbituril a (R ═ CH)2)nSO3A, a ═ H, n ═ 3); (b) ring-opened cucurbituril a (R ═ CH)2)nSO3A, a ═ H, n ═ 3) with ethyl vanillin; (c) ethyl vanillin. After the inclusion compound is formed, H-4 of ethyl vanillin generates obvious high field shift (delta is 0.30ppm), and H-1, 2 and 3 also respectively shift to high fields by 0.14ppm, 0.35ppm and 0.05 ppm. The change in chemical shift evidences the formation of the inclusion complex.
As shown in FIG. 2, 2D-ROESY spectrum analysis of the clathrate compound in this example was conducted. H-1,3 and 6 on the ethyl vanillin have significant related signals with H-b ', c ' and D ' inside the cavity of the ring-opened cucurbituril I and H-g hydrogen protons on the propane sulfonic acid alkyl on the aromatic ring of the ring-opened cucurbituril, so that the formation of the clathrate is further judged according to 2D-ROESY.
Example 2
1.341g (1mmol) of anion ring-opened cucurbituril a (R ═ CH2)nSO3Dissolving solid powder of A, A ═ H, n ═ 1) in 15ml, heating at 60 deg.C and stirring for 60min to dissolve completely, stopping heating, allowing the solution to cool to room temperature, dissolving vanillin 0.456g (3mmol) in 5ml of ethanol, and adding to Ring-opened cucurbituril a (R ═ (CH ═ 1)2)nSO3A, A ═ H, n ═ 1) in an aqueous solution, vigorously stirred at 50 ℃ for 72 hours, filtered to remove insoluble matter, and the filtrate was lyophilized to give anion ring-opened cucurbituril I (R ═ CH (CH)2)nSO3A, a ═ H, n ═ 1) and the target product of vanillin inclusion compound, the yield was 97%.
As shown in fig. 3, the X-ray diffraction spectrum of the clathrate in this example was analyzed by contrast. (a) Ring-opened cucurbituril a (R ═ CH)2)nSO3A, a ═ H, n ═ 1); (b) ring-opened cucurbituril a (R ═ CH)2)nSO3A, a ═ H, n ═ 1) with vanillin; (c) vanillin is prepared. Forming inclusion compound and then opening cucurbituril a (R ═ CH)2)nSO3The characteristic peaks of A, A ═ H, n ═ 1) and ethyl vanillin almost disappeared, andshows a new amorphous structure, indicating that the ethyl vanillin molecule is linked with ring-opened cucurbituril a (R ═ CH2)nSO3A, A ═ H, n ═ 1) form inclusion compound.
Example 3
1.541g (1mmol) of anion ring-opened cucurbituril a (R ═ CH2)nSO3A, A ═ Na, n ═ 3) solid powder was dissolved in 15ml, heated at 50 ℃ and stirred for 45min to completely dissolve it, heating was stopped, the solution was cooled to room temperature, and then 0.830g (5mmol) of ethyl vanillin was added directly to anion ring-opened cucurbituril a (R ═ CH ═ s (CH ═ 3mmol)2)nSO3Stirring A, A ═ Na, n ═ 3) in water solution, reacting at 20 deg.C for 36h, filtering to remove insoluble matter, concentrating filtrate under reduced pressure, and drying to obtain anion ring-opened cucurbituril a (R ═ CH (CH ═ 3)2)nSO3A, a ═ Na, n ═ 3) and the target product of the ethyl vanillin clathrate in a yield of 98%.
As shown in fig. 4, the heat release analysis chart for the clathrate in this example. The inclusion compound is relatively stable at 25 ℃, and only a small amount of ethyl vanillin is released from the inclusion compound during the test period; at 60 ℃, the heat release efficiency of the ethyl vanillin in the inclusion compound is weak; under the environment of 120 ℃, the release rate of the ethyl vanillin in the inclusion compound is obviously increased along with time, which shows that the inclusion compound has good thermal response performance.
Example 4
1.509g (1mmol) of anionic ring-opened cucurbituril a (R ═ CH)2)nSO3Dissolving solid powder of A, A ═ H, n ═ 4) in 15ml, heating at 20 deg.C and stirring for 60min to make it completely dissolve, stopping heating, cooling the solution to room temperature, dissolving vanillin 1.328g (8mmol) in 10ml of dimethyl sulfoxide, and adding to ring-opened cucurbituril a (R ═ CH (8mmol)2)nSO3A, A ═ H, n ═ 4) in an aqueous solution, vigorously stirred at 40 ℃ for 72 hours, filtered to remove insoluble matter, and the filtrate was concentrated under reduced pressure and dried to give anion ring-opened cucurbituril a (R ═ CH (CH)2)nSO3A, a ═ H, n ═ 4) and vanillin clathrate target products, at a yield of 95%.
As shown in FIG. 5, the Thermal Gravimetric Analysis (TGA) of the clathrate in this exampleAnalyzing the graph: (a) anion ring-opened cucurbituril a (R ═ CH2)nSO3A, a ═ H, n ═ 4) with vanillin; (b) anion ring-opened cucurbituril a (R ═ CH2)nSO3A physical mixture of a, a ═ H, n ═ 4) with vanillin; (c) anion ring-opened cucurbituril a (R ═ CH2)nSO3A, a ═ H, n ═ 4); (d) vanillin is prepared. It can be seen from the graph that the four curves show different downward trends with increasing temperature, with the highest mass retention of the clathrate. These data indicate that vanillin opens with the anion cucurbituril a (R ═ CH (CH)2)nSO3A, a ═ H, and n ═ 4) form inclusion compounds, and their thermal stability is significantly improved, which cannot be achieved by simple physical mixing.
Example 5
1.653g (1mmol) of anionic ring-opened cucurbituril a (R ═ CH)2)nSO3Dissolving a, a ═ Na, n ═ 5) solid powder in 15ml, heating at 50 ℃ and stirring for 45min to completely dissolve it, stopping heating, allowing the solution to cool to room temperature, then dissolving 0.498g (3mmol) of ethyl vanillin in 5ml of diethyl ether, and adding to ring-opened cucurbituril a (R ═ (CH ═ 5)2)nSO3A, A ═ Na, n ═ 5) in an aqueous solution, vigorously stirred at 20 ℃ for 24 hours, filtered to remove insoluble matter, and the filtrate was concentrated under reduced pressure and dried to give anion ring-opened cucurbituril a (R ═ CH (CH)2)nSO3A, a ═ Na, n ═ 5) and the desired product of ethylvanillin inclusion compound in a yield of 97%.
Example 6
1.734g (1mmol) of anionic ring-opened cucurbituril b (R ═ CH2)nSO3Dissolving a, a ═ H, n ═ 3) solid powder in 15ml, heating at 30 ℃ and stirring for 30min to completely dissolve it, stopping heating, allowing the solution to cool to room temperature, and then adding 1.520g (10mmol) of ethyl vanillin directly to anion ring-opened cucurbituril b (R ═ CH (CH ═ 3)2)nSO3A, A ═ H, n ═ 3) in an aqueous solution, vigorously stirred at 20 ℃ for 1H, filtered to remove insoluble substances, and the filtrate was concentrated under reduced pressure and dried to give anion ring-opened cucurbituril b (R ═ CH (CH) and2)nSO3a, a ═ H, n ═ 3) and objects of ethylvanillin clathrateThe product was obtained in 95% yield.
As shown in fig. 6, the nmr hydrogen spectrum of the clathrate prepared in this example was analyzed: (a) anion ring opening cucurbituril b (R ═ CH2)nSO3A, a ═ H, n ═ 3); b) anion ring opening cucurbituril b (R ═ CH2)nSO3A, a ═ H, n ═ 3) with ethyl vanillin; c) ethyl vanillin. After the clathrate compound is formed, the proton chemical shift of the ethyl vanillin is obviously changed, and the original sharp peak shape is changed to be short and flat, which shows that the anion ring-opening cucurbituril b (R ═ (CH) ═ is formed2)nSO3A, a ═ H, n ═ 3) has formed a clathrate with ethyl vanillin.
Example 7
1.641g (1mmol) of anionic ring-opened cucurbituril b (R ═ CH2)nSO3A, a ═ Na, n ═ 8) solid powder was dissolved in 15ml, heated at 50 ℃ and stirred for 60min to completely dissolve it, heating was stopped, the solution was cooled to room temperature, and then 0.249g (1.5mmol) of ethyl vanillin was added directly to anion ring-opened cucurbituril b (R ═ CH (CH ═ 8)2)nSO3Stirring A, A ═ Na, n ═ 8) in water solution at 90 deg.C for 172h, filtering to remove insoluble matter, concentrating the filtrate under reduced pressure, and drying to obtain anion ring-opened cucurbituril b (R ═ CH (CH)2)nSO3A, a ═ Na, n ═ 8) and ethyl vanillin, in 98% yield.
As shown in fig. 7, the comparative fourier analysis chart of the inclusion compound prepared in this example: (a) anion ring opening cucurbituril b (R ═ CH2)nSO3A, a ═ Na, n ═ 8) and ethyl vanillin; (b) anion ring opening cucurbituril b (R ═ CH2)nSO3A, a ═ Na, n ═ 8) and ethyl vanillin; (c) ethyl vanillin; (d) anion ring opening cucurbituril b (R ═ CH2)nSO3A, a ═ Na, n ═ 8). The FT-IR spectrum of the physical mixture shows an approximate superposition of the spectra of both species, with the absorption peaks of both species remaining almost entirely. On the contrary, after the inclusion compound is formed, the ethyl vanillin is added at 1681, 1586, 1410 and 1102cm-1The peak disappears or is obviously weakenedThese absorption bands are strongly and widely separated by a ring-opening cucurbituril b (R ═ CH)2)nSO3A, a ═ Na, n ═ 8). This change may be associated with ring-opened cucurbituril b (R ═ (CH)2)nSO3A, a ═ Na, n ═ 8) is involved in intramolecular hydrogen bonding with ethyl vanillin.
Example 8
1.765g (1mmol) of anionic ring-opened cucurbituril b (R ═ CH)2)nSO3Dissolving a, a ═ Na, n ═ 7) solid powder in 15ml, heating at 100 ℃ and stirring for 60min to completely dissolve it, stopping heating, allowing the solution to cool to room temperature, and then adding 0.415g (2.5mmol) of ethyl vanillin directly to anion ring-opened cucurbituril b (R ═ CH (CH ═ 7 mmol)2)nSO3Stirring A, Na and n 7 in water at 40 deg.C for 48 hr, filtering to remove insoluble substance, and freeze drying to obtain anion ring-opened cucurbituril b (R ═ CH (7))2)nSO3A, Na, n-7) and ethyl vanillin in 97% yield.
Example 9
1.621g (1mmol) of anionic ring-opened cucurbituril b (R ═ CH)2)nSO3Dissolving solid powder of A, A ═ H, n ═ 6) in 15ml, heating at 80 deg.C and stirring for 30min to dissolve completely, stopping heating, allowing the solution to cool to room temperature, and adding vanillin 0.608g (4mmol) directly to anion ring-opened cucurbituril b (R ═ CH ═ H, n ═ 6)2)nSO3Stirring A, A ═ H, n ═ 6) in water solution, reacting at 20 deg.C for 72H, filtering to remove insoluble matter, freeze drying to obtain anion ring-opened cucurbituril b (R ═ CH (CH)2)nSO3A, a ═ H, n ═ 6) and vanillin, the target product, at a yield of 96%.
Example 10
1.585g (1mmol) of anionic ring-opened cucurbituril c (R ═ CH2)nSO3Dissolving a, a ═ Na, n ═ 2) solid powder in 15ml, heating at 40 ℃ and stirring for 30min to completely dissolve it, stopping heating, allowing the solution to cool to room temperature, and then adding 0.664g (4mmol) of ethyl vanillin directly to anion ring-opened cucurbituril c (R ═ CH (CH ═ 2)2)nSO3A, a ═ Na, n ═ 2) in an aqueous solution at 30 ℃After the reaction was vigorously stirred for 96 hours, insoluble substances were removed by filtration, and the residue was lyophilized to obtain an anion ring-opened cucurbituril c (R ═ CH2)nSO3A, a ═ Na, n ═ 2) and ethyl vanillin, in 96% yield.
Example 11
1.529g (1mmol) of anionic ring-opened cucurbituril c (R ═ CH)2)nSO3Dissolving A, A ═ Na, n ═ 6) solid powder in 20ml, heating at 50 deg.C and stirring for 30min to dissolve completely, stopping heating, allowing the solution to cool to room temperature, adding vanillin 1.368g (9mmol) to anion ring-opened cucurbituril c (R ═ CH (CH ═ 6) after adding 20ml ethanol2)nSO3Stirring A, A ═ Na, n ═ 6) in water solution, reacting at 40 deg.C for 144h, filtering to remove insoluble matter, freeze drying to obtain anion ring-opened cucurbituril c (R ═ CH (CH ═ 6)2)nSO3A, a ═ Na, n ═ 6) and vanillin, the target product, at a yield of 96%.
As shown in fig. 8, the heat release profile of the inclusion compound prepared in this example at different temperatures: the inclusion compound was relatively stable at 25 c and only a small amount of vanillin was released from the inclusion compound during the test. At 60 ℃, the content of vanillin in the inclusion compound is respectively maintained at 70.4% after 72 hours, which shows that the heat release efficiency of the two inclusion compounds at 60 ℃ is weak. Under the environment of 120 ℃, the release rate of vanillin in the inclusion compound is obviously increased along with time, and the retention rate of vanillin in the experimental time is only 32.1%. This indicates that the clathrate in this example has good performance under thermal response.
Example 12
1.834g (1mmol) of anionic ring-opened cucurbituril c (R ═ CH)2)nSO3Dissolving a, a ═ H, n ═ 8) solid powder in 15ml, heating at 60 ℃ and stirring for 50min to completely dissolve it, stopping heating, allowing the solution to cool to room temperature, then adding 0.166g (1mmol) of ethyl vanillin to 5ml of ethyl acetate, and then adding to anion ring-opened cucurbituril c (R ═ (CH ═ 8)2)nSO3Stirring A, A ═ H, n ═ 8) in water solution, reacting at 20 deg.C for 150H, filtering to remove insoluble matter, freeze drying to obtain anion ring-opened cucurbituril c (R ═ (CH ═ 8)2)nSO3A, H, n-8) and ethyl vanillin in 96% yield.
Example 13
1.753g (1mmol) of anion ring-opened cucurbituril c (R ═ CH2)nSO3Dissolving A, A ═ Na, n ═ 5) solid powder in 15ml, heating at 80 deg.C and stirring for 45min to dissolve completely, stopping heating, allowing the solution to cool to room temperature, dissolving vanillin 0.608g (4mmol) in 10ml of methanol, and adding to anion ring-opened cucurbituril c (R ═ (CH ═ 5)2)nSO3Stirring A, A ═ Na, n ═ 5) in water solution at 20 deg.C for 168h, filtering to remove insoluble matter, and freeze drying to obtain anion ring-opened cucurbituril c (R ═ CH (CH ═ 5)2)nSO3A, a ═ Na, n ═ 5) and vanillin, the target product, at a yield of 96%.
As shown in fig. 9, the Thermogravimetric (TGA) analysis profile of the clathrate prepared in this example: (a) anion ring opening cucurbituril c (R ═ CH2)nSO3A, a ═ Na, n ═ 5) with vanillin; (b) anion ring opening cucurbituril c (R ═ CH2)nSO3A, a ═ Na, n ═ 5) and vanillin; (c) anion ring opening cucurbituril c (R ═ CH2)nSO3A, a ═ Na, n ═ 5); (d) vanillin is prepared. It can be seen from the graph that as the temperature increases, the four curves show different descending trends, and the mass retention rates in the range of 400-700 ℃ are sequentially from high to low: a > b > c > d. These data indicate that vanillin opens with the anion cucurbituril c (R ═ CH (CH)2)nSO3A, a ═ Na, and n ═ 5) form inclusion compounds, and the thermal stability is significantly improved.
The preparation or synthesis methods not described in the present application are prior art and thus are not described in detail.
The anion ring-opening cucurbituril and vanillin type spice inclusion compound prepared by the invention can obviously improve the thermal stability of vanillin type spices, can be applied to the fields of essence spices, tobacco, cosmetics, food, nutritional health-care products and the like, can realize the slow release and controlled release of the vanillin type spice, and is more stable and safer.
Although the present invention has been described with reference to the above embodiments, it should be understood that the present invention is not limited thereto, and various changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the present invention.

Claims (10)

1. The inclusion compound of anion ring-opening cucurbituril and vanillin spice is characterized in that the inclusion compound is formed by the reaction of vanillin spice and anion ring-opening cucurbituril, and the structural formula of the inclusion compound is one of six types as follows:
Figure FDA0003498547970000011
2. a clathrate of anion-opening cucurbiturils and vanillin based fragrances in claim 1, wherein the anion-opening cucurbiturils are selected from one of the following compounds:
Figure FDA0003498547970000021
wherein R is ═ CH2)nSO3A, wherein A is Na or H, and n is 1-8.
3. A clathrate of anion-opening cucurbiturils and vanillin based fragrance as claimed in claim 2, characterised in that chain lengths of substituent groups of anion-opening cucurbiturils are n ═ 2 and 3, i.e. R ═ CH (CH ═ c2)2SO3A and R ═ CH2)3SO3A。
4. A clathrate of anion-opening cucurbituril and vanillin fragrance as claimed in claim 1, wherein the vanillin fragrance is vanillin or ethyl vanillin.
5. A process for the preparation of a clathrate of anion-opening cucurbiturils and vanillin based fragrance according to any one of claims 1 to 4, comprising the steps of:
(1) adding the anion ring-opening cucurbituril solid powder into a reaction kettle, adding a proper amount of pure water, heating, and stirring for 30-60 min to completely dissolve the solid powder;
(2) stopping heating after dissolution, cooling the solution to room temperature, directly adding vanillin spices or dissolving vanillin spices in an organic solvent, adding the solution into an aqueous solution of an anion ring-opening cucurbituril, and violently stirring and reacting at 0-90 ℃ for 1-192 hours;
(3) filtering to remove insoluble substances, and drying the filtrate to obtain the target product of the clathrate of the anion ring-opening cucurbituril and the vanillin spice.
6. The method for preparing the inclusion compound of anion ring-opening cucurbituril and vanillin spice according to claim 5, wherein the temperature for heating the anion ring-opening cucurbituril in the step (1) is 30-100 ℃.
7. The preparation method of the clathrate compound of anion ring-opening cucurbituril and vanillin spice according to claim 5, wherein the molar ratio of the anion ring-opening cucurbituril to the vanillin spice in the step (2) is 1 (1-10); the organic solvent is one or more of methanol, ethanol, petroleum ether, ethyl acetate, dimethyl sulfoxide, N-dimethylformamide, dichloromethane, tetrahydrofuran or acetone.
8. The method of claim 7, wherein the organic solvent is selected from the group consisting of ethanol, dimethylsulfoxide, N-dimethylformamide, and tetrahydrofuran.
9. The method for preparing the clathrate of anion ring-opened cucurbituril and vanillin type flavor according to claim 5, wherein the drying manner in the step (3) is freeze drying, reduced pressure concentration drying or spray drying.
10. Use of a clathrate of anion-opening cucurbituril and vanillin based flavor according to any one of claims 1 to 4 in the preparation of a flavor and fragrance, tobacco, cosmetic, food or nutraceutical.
CN202210121773.XA 2022-02-09 2022-02-09 Clathrate compound of anion ring-opening cucurbituril and vanillin spice and preparation method and application thereof Pending CN114456183A (en)

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WO2014077640A1 (en) * 2012-11-16 2014-05-22 Postech Academy-Industry Foundation Composition for slow emission of fragrance comprising complexes of cucurbituril and fragrance molecule
CN108601958A (en) * 2016-02-15 2018-09-28 爱客多有限公司 Pro-perfume compositions
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