CN111303995A - Clathrate compound of anion ring-opening cucurbituril and nicotine substances as well as preparation method and application thereof - Google Patents
Clathrate compound of anion ring-opening cucurbituril and nicotine substances as well as preparation method and application thereof Download PDFInfo
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- CN111303995A CN111303995A CN202010137573.4A CN202010137573A CN111303995A CN 111303995 A CN111303995 A CN 111303995A CN 202010137573 A CN202010137573 A CN 202010137573A CN 111303995 A CN111303995 A CN 111303995A
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- 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
- C11B9/0069—Heterocyclic compounds
- C11B9/0092—Heterocyclic compounds containing only N as heteroatom
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- 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
- A24B15/24—Treatment of tobacco products or tobacco substitutes by extraction; Tobacco extracts
- A24B15/26—Use of organic solvents for extraction
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Abstract
The invention discloses an inclusion compound of anion ring-opened cucurbituril and nicotine substances, a preparation method and application thereof, wherein the nicotine substances and the anion ring-opened cucurbituril form an inclusion reaction; according to the invention, the anion ring-opening cucurbituril molecule is provided with the C-shaped cavity, so that an inclusion effect can be formed by matching the size of the cavity with nicotine substances, and meanwhile, the ionic property of the anion ring-opening cucurbituril molecule and the basic group of the nicotine substances have dipolar interaction, so that the binding property of the two substances is enhanced, and the thermal stability of the nicotine substances is enhanced. The nicotine inclusion compound can realize the slow release and the controlled release of nicotine in the application process of tobacco, tobacco products, electronic cigarettes and heating non-burning cigarettes, continuously keeps the physiological satisfaction of smokers and is safer. The inclusion compound can be applied to the industries of flavors and fragrances and tobacco.
Description
Technical Field
The invention relates to the field of preparation of tobacco flavors and fragrances, in particular to an inclusion compound of anion ring-opening cucurbituril and nicotine substances, a preparation method and application thereof.
Background
Nicotine is an alkaloid contained in Solanaceae plants (Solanum), and when smoking, nicotine is absorbed into body with smoke, enters blood, and binds with acetylcholine receptor, and has effects of exciting and relaxing, and reducing anxiety and stress response. The tobacco and the products thereof can provide the smokers with proper physiological intensity and beautiful flavor only if containing proper nicotine.
Nicotine in the cigarette is mainly derived from tobacco leaf raw materials, the nicotine content of different varieties, parts and the like of the tobacco leaf raw materials is different, and the nicotine content can be adjusted through a leaf group formula or modified through adding nicotine essence and spice; nicotine in new tobacco (including e-liquid and heated non-burning cartridges) is mainly achieved by adding free nicotine or nicotine salt extracted from tobacco; tobacco products such as reconstituted tobacco and the like also need to be added with a certain amount of nicotine substances to ensure the smoking quality. The nicotine substance is also applied to modern biological pesticides, is used for preventing and controlling pests, has the effects of contact poisoning, stomach poisoning and fumigation, and has a certain ovicidal effect.
In the smoking process of tobacco, novel tobacco and tobacco products, the externally added nicotine is volatile and has insufficient persistence, so that the smoking feeling is influenced; in the production process of tobacco products, the directly added nicotine is more lost by heating and has low processing resistance; in the use process of the nicotine pesticide, the nicotine is volatile, so the lasting period is short.
Therefore, the preparation and application of the inclusion compound of the anion ring-opening cucurbituril and the nicotine substance can effectively control the volatility and stability of nicotine in the process, realize slow release and controlled release and have practical application value, and the research of the method is not reported.
Disclosure of Invention
The invention aims to provide an anion ring-opening cucurbituril and nicotine substance clathrate compound, a preparation method and application thereof, the clathrate compound has good stability and high binding constant, and the release of nicotine substances in the clathrate compound can be realized by controlling temperature.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of an inclusion compound of anion ring-opened cucurbituril and nicotine substances is characterized in that the inclusion compound is formed by the inclusion reaction of the nicotine substances and the anion ring-opened cucurbituril, and the preparation method comprises the following steps: adding a type of anion ring-opening cucurbituril solid powder into a reaction kettle or a round-bottom flask, then adding a proper amount of pure water, stirring for 5-30 min at 40-100 ℃ to dissolve the solid, stopping heating and cooling to room temperature after the solid is completely dissolved, then dissolving nicotine and analogues thereof into water or an organic solvent or directly adding the nicotine and analogues thereof into a type of anion ring-opening cucurbituril solution, stirring the mixture at 20-60 ℃ for at least 6h, and then concentrating and drying under reduced pressure at 40-60 ℃, spray drying or freeze drying to obtain a nicotine substance inclusion compound; wherein the feeding molar ratio of the nicotine substance to the anionic ring-opening cucurbituril is 1-10: 1.
In a preferred embodiment of the present invention, the feeding molar ratio of the nicotine substance to the anionic ring-opened cucurbituril is 2.5: 1.
In the present invention, the anionic ring-opened cucurbiturils are selected from
Wherein R is (CH)2)nSO3Na, wherein n is 2,3 or 4.
In the invention, the structural formula of the nicotine substance is shown as
X is selected from
Namely the following substances:
further, the organic solvent is methanol, ethanol, dimethyl sulfoxide, N-dimethylformamide, acetone, chloroform or tetrahydrofuran.
The results of the clathrate of nicotine and anion ring-opened cucurbituril I, the clathrate of nornicotine and anion ring-opened cucurbituril II, and the clathrate of neonicotine and anion ring-opened cucurbituril III prepared by the preparation method are shown in figures 1-3 by using magnetic resonance hydrogen spectrum detection, and prove that the new clathrate is obtained by the method.
The thermal stability of the nicotine and anion ring-opening cucurbituril I inclusion compound prepared by the preparation method is verified at 60 ℃ and 120 ℃ respectively, and then the thermal stability is performed respectively1The HNMR researches the release degree of the nicotine substances in the inclusion compound, and the results are shown in figures 4-5, and the figure shows that the inclusion compound of the nicotine substances and the analogues thereof does not release the nicotine substances at 60 ℃ and 120 ℃, which can prove that the inclusion compound has good thermal stability.
The inclusion compound prepared by the preparation method has excellent slow release effect, can be applied to the preparation of flavors and fragrances, tobacco industry and biological pesticides, and is used as a slow release type nicotine substance, particularly the addition of nicotine in the preparation process of novel tobacco.
The beneficial technical effects of the invention are as follows: according to the invention, the anion ring-opening cucurbituril molecule is provided with the C-shaped cavity, so that an inclusion effect can be formed by matching the size of the cavity with nicotine substances, and meanwhile, the ionic property of the anion ring-opening cucurbituril molecule and the basic group of the nicotine substances have dipolar interaction, so that the binding property of the two substances is enhanced, and the thermal stability of the nicotine substances is enhanced. The nicotine inclusion compound can realize the slow release and the controlled release of nicotine in the application process of electronic cigarettes and heating non-combustible cigarettes, continuously keep the physiological satisfaction of smokers, is safer, and can be applied to the industries of essence, spice and tobacco; the preparation method is simple, convenient and feasible, has mild conditions and is suitable for industrial production.
Drawings
FIG. 1 shows the nuclear magnetic resonance hydrogen spectrum of the clathrate of nicotine and anion ring-opening cucurbituril I (I) ((1H NMR) comparison plot, wherein (a) nicotine; (b) nicotine and anion ring-opening cucurbituril clathrate compound I (the molar ratio is 1: 1); (c) nicotine and anion ring-opening cucurbituril I clathrate (molar ratio is 1: 2); (d) anion ring-opening cucurbituril I.
FIG. 2 shows NMR spectra of nornicotine and anion ring-opened cucurbituril II clathrate released at 60 deg.C for different time1H NMR) comparison plot, wherein (a) nornicotine and anionic ring-opened cucurbituril ii inclusion compounds were released at 60 ℃ for 18H; (b) the cotinine and the anion ring-opening cucurbituril II inclusion compound are released for 40min at 60 ℃; (c) untreated cotinine substances and an anion ring-opening cucurbituril II clathrate compound.
FIG. 3 shows NMR spectra of neonicotinoid and anion ring-opened cucurbituril III clathrate released at 120 deg.C for different time1H NMR) comparison plot, wherein (a) the neonicotinoid and anionic ring-opened cucurbituril iii inclusion compounds were released at 120 ℃ for 18H; (b) releasing the N-nitrosonornicotine and anion ring-opening cucurbituril III clathrate compound for 40min at 120 ℃; (c) untreated N-nitrosonornicotine and anionic ring-opened cucurbituril iii clathrates.
Figure 460 ℃ profile of nicotine release;
figure 5120 ℃ profile of nicotine release results;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
0.154mmol of anionic ring-opened cucurbituril I (R is (CH)2)nSO3Na, n is 3)Dissolving in 25mL of distilled water, stirring at 20 ℃ until dissolving, adding 0.16mmol of nicotine into the anion ring-opened cucurbituril solution, stirring at 25 ℃ for 7 days, performing reduced pressure concentration at 40 ℃ to remove water, and performing vacuum drying to obtain the anion ring-opened cucurbituril I and nicotine clathrate compound with the yield of 96%.
Example 2
0.154mmol of anionic ring-opened cucurbituril I (R is (CH)2)nSO3Na and n are 2), dissolving in 12mL of distilled water, stirring at 60 ℃ until the solution is dissolved, adding 0.8mmol of nornicotine into the anion ring-opened cucurbituril solution, stirring at 20 ℃ for 6h, performing reduced pressure concentration at 20 ℃ to remove water, and performing vacuum drying to obtain the clathrate of the anion ring-opened cucurbituril I and the nornicotine, wherein the yield is 97%.
Example 3
0.154mmol of anionic ring-opened cucurbituril I (R is (CH)2)nSO3Na and n are 4) is dissolved in 40mL of distilled water, the mixture is stirred to be dissolved at 40 ℃, 0.16mmol of dehydro-demethyl nicotine is added into the anion ring-opening cucurbituril solution, the mixture is stirred for 3 days at 60 ℃, water is removed by decompression and concentration at 60 ℃, and the clathrate compound of the anion ring-opening cucurbituril I and the dehydro-demethyl nicotine is prepared by vacuum drying, wherein the yield is 95%.
Example 4
0.154mmol of anionic ring-opened cucurbituril I (R is (CH)2)nSO3Na and n are 3), dissolving in 6mL of distilled water, stirring at 25 ℃ until the solution is dissolved, adding 0.16mmol of demethyldiennicotin into the anion ring-opening cucurbituril solution, stirring at 40 ℃ for 18 hours, performing reduced pressure concentration at 40 ℃ to remove water, and performing vacuum drying to obtain the inclusion compound of the anion ring-opening cucurbituril I and the demethyldiennicotin, wherein the yield is 98%.
Example 5
0.154mmol of anionic ring-opened cucurbituril II (R is (CH)2)nSO3Na and n are 3) is dissolved in 25mL distilled water, stirred at 20 deg.C until dissolved, 0.16mmol nicotine is added to the anion ring-opened cucurbituril solution, stirred at 25 deg.C for 7 days, concentrated at 40 deg.C under reduced pressure to remove water, and vacuum concentratedDrying to obtain the clathrate compound of the anion ring-opening cucurbituril II and the nicotine, wherein the yield is 99%.
Example 6
0.154mmol of anionic ring-opened cucurbituril II (R is (CH)2)nSO3Na and n are 3), dissolving in 6mL of distilled water, stirring at 25 ℃ until the solution is dissolved, adding 0.16mmol of diene nicotine into the anion ring-opening cucurbituril solution, stirring at 40 ℃ for 18 hours, performing reduced pressure concentration at 40 ℃ to remove water, and performing vacuum drying to obtain the anion ring-opening cucurbituril II and diene nicotine clathrate compound, wherein the yield is 98%.
Example 7
0.154mmol of anionic ring-opened cucurbituril II (R is (CH)2)nSO3Na and n are 2), dissolving in 12mL of distilled water, stirring at 60 ℃ until the solution is dissolved, adding 0.8mmol of neonicotine into the anion ring-opening cucurbituril solution, stirring at 20 ℃ for 6h, performing reduced pressure concentration at 20 ℃ to remove water, and performing vacuum drying to obtain the clathrate compound of the anion ring-opening cucurbituril II and the neonicotine, wherein the yield is 97%.
Example 8
0.154mmol of anionic ring-opened cucurbituril II (R is (CH)2)nSO3Na and n are 4) is dissolved in 40mL of distilled water, the mixture is stirred to be dissolved at 40 ℃, 0.16mmol of methyl neonicotinoid is added into the anion ring-opening cucurbituril solution, the mixture is stirred for 3 days at 60 ℃, water is removed by decompression and concentration at 60 ℃, and the inclusion compound of the anion ring-opening cucurbituril II and the methyl neonicotinoid is prepared by vacuum drying, wherein the yield is 98%.
Example 9
0.154mmol of anionic ring-opened cucurbituril III (R is (CH)2)nSO3Na and n are 3), dissolving in 25mL of distilled water, stirring at 20 ℃ until the solution is dissolved, adding 0.16mmol of nicotine into the anion ring-opening cucurbituril solution, stirring at 25 ℃ for 7 days, performing reduced pressure concentration at 40 ℃ to remove water, and performing vacuum drying to obtain the anion ring-opening cucurbituril III and nicotine clathrate compound with the yield of 96%.
Example 10
0.154mmol of anionic ring-opened cucurbituril III (R is (CH)2)nSO3Na and n are 2), dissolving in 12mL of distilled water, stirring at 60 ℃ until the solution is dissolved, adding 0.8mmol of denitrified nicotine into the anion ring-opened cucurbituril solution, stirring at 20 ℃ for 6h, performing reduced pressure concentration at 20 ℃ to remove water, and performing vacuum drying to obtain the clathrate compound of the anion ring-opened cucurbituril III and the denitrified nicotine, wherein the yield is 97%.
Example 11
0.154mmol of anionic ring-opened cucurbituril III (R is (CH)2)nSO3Na and N are 3), dissolving in 6mL of distilled water, stirring at 25 ℃ until the solution is dissolved, adding 0.16mmol of N-methyl denitrogenated neonicotine into the anion ring-opening cucurbituril solution, stirring at 40 ℃ for 18 hours, performing reduced pressure concentration at 40 ℃ to remove water, and performing vacuum drying to obtain the inclusion compound of the anion ring-opening cucurbituril III and the N-methyl denitrogenated neonicotine, wherein the yield is 98%.
Example 12
0.154mmol of anionic ring-opened cucurbituril III (R is (CH)2)nSO3Na and n are 4) is dissolved in 40mL of distilled water, the mixture is stirred to be dissolved at 40 ℃, 0.16mmol of 2,3 '-bipyridine is added into the anion ring-opening cucurbituril solution, the mixture is stirred for 3 days at 60 ℃, water is removed by decompression concentration at 60 ℃, and the clathrate compound of the anion ring-opening cucurbituril III and the 2, 3' -bipyridine is prepared by vacuum drying, wherein the yield is 95%.
Claims (10)
1. A preparation method of an inclusion compound of anion ring-opening cucurbituril and nicotine substances is characterized in that the inclusion compound is formed by the inclusion reaction of nicotine substances and anion ring-opening cucurbituril, and the preparation method comprises the following steps: adding a type of anion ring-opening cucurbituril solid powder into a reaction kettle or a round-bottom flask, then adding a proper amount of pure water, stirring for 5-30 min at 40-100 ℃ to dissolve the solid, stopping heating and cooling to room temperature after the solid is completely dissolved, then dissolving nicotine and analogues thereof into water or an organic solvent or directly adding the nicotine and analogues thereof into a type of anion ring-opening cucurbituril solution, stirring the mixture at 20-60 ℃ for at least 6h, and then concentrating and drying under reduced pressure at 40-60 ℃, spray drying or freeze drying to obtain a nicotine substance inclusion compound; wherein the feeding molar ratio of the nicotine substance to the anionic ring-opening cucurbituril is 1-10: 1.
2. The preparation method according to claim 1, wherein the feeding molar ratio of the nicotine-based substance to the anionic ring-opened cucurbituril is 2.5: 1.
3. The method according to claim 1, wherein the anionic ring-opened cucurbituril is selected from the group consisting of cucurbiturils
Wherein R is (CH)2)nSO3Na, wherein n is 2,3 or 4.
4. The method according to claim 1, wherein the nicotinic substance has the structural formula
5. The method according to claim 4, wherein X is selected from the group consisting of
6. The method according to claim 1, wherein the organic solvent is methanol, ethanol, dimethylsulfoxide, N-dimethylformamide, acetone, chloroform or tetrahydrofuran.
7. A clathrate compound produced by the production method described in any one of claims 1 to 6.
8. The use of the clathrate compound according to claim 7 in biopesticides.
9. Use of the inclusion compound according to claim 7 in tobacco.
10. A tobacco product comprising the inclusion compound prepared by the preparation method according to any one of claims 1 to 6.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112362624A (en) * | 2020-11-10 | 2021-02-12 | 云南中烟工业有限责任公司 | Supermolecule fluorescence analysis method for detecting alcohol perfume compounds |
| CN114057690A (en) * | 2021-11-30 | 2022-02-18 | 昆明理工大学 | Clathrate compound of semi-cucurbit [6] uril and tobacco alkaloid, preparation method and application thereof |
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| CN108771675A (en) * | 2018-07-19 | 2018-11-09 | 昆明理工大学 | The inclusion compound and preparation method thereof of artemisinin-based drug and open loop Cucurbituril |
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| CN108771675A (en) * | 2018-07-19 | 2018-11-09 | 昆明理工大学 | The inclusion compound and preparation method thereof of artemisinin-based drug and open loop Cucurbituril |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112362624A (en) * | 2020-11-10 | 2021-02-12 | 云南中烟工业有限责任公司 | Supermolecule fluorescence analysis method for detecting alcohol perfume compounds |
| CN114057690A (en) * | 2021-11-30 | 2022-02-18 | 昆明理工大学 | Clathrate compound of semi-cucurbit [6] uril and tobacco alkaloid, preparation method and application thereof |
| CN114057690B (en) * | 2021-11-30 | 2024-02-27 | 昆明理工大学 | Clathrate compound of semi-cucurbit [6] urils and tobacco alkaloids, and preparation method and application thereof |
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