CN111303995B - 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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- CN111303995B CN111303995B CN202010137573.4A CN202010137573A CN111303995B CN 111303995 B CN111303995 B CN 111303995B CN 202010137573 A CN202010137573 A CN 202010137573A CN 111303995 B CN111303995 B CN 111303995B
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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 with nicotine substances due to the size of the cavity, 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 realize the purpose, the invention adopts the technical scheme that: 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 specifically comprises the following steps: adding a kind of anion ring-opening cucurbituril solid powder into a reaction kettle or a round-bottom flask, then adding a proper amount of pure water into the reaction kettle or the round-bottom flask, stirring the mixture at 40-100 ℃ for 5-30 min to dissolve the solid, stopping heating and cooling the mixture 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 kind of anion ring-opening cucurbituril solution, stirring the mixture at 20-60 ℃ for at least 6h, and then carrying out reduced pressure concentration drying, spray drying or freeze drying at 40-60 ℃ to obtain a nicotine substance inclusion compound; wherein the feeding molar ratio of the nicotine substance to the anion ring-opening cucurbituril is 1-10.
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.
In the present invention, the anionic ring-opened cucurbiturils are selected from
Wherein R is (CH) 2 ) n SO 3 Na, where n =2,3 or 4.
In the invention, the structural formula of the nicotine substance is shown in the specification
X is selected from
Namely the following substances:
further, the organic solvent is methanol, ethanol, dimethyl sulfoxide, N-dimethylformamide, acetone, chloroform or tetrahydrofuran.
The clathrate compound of nicotine and anion ring-opened cucurbituril I, the clathrate compound of nornicotine and anion ring-opened cucurbituril II, and the clathrate compound of neonicotine and anion ring-opened cucurbituril III prepared by the preparation method are detected by using a magnetic resonance hydrogen spectrum, and the results are shown in figures 1-3, thereby proving that the new clathrate compound 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 respectively verified at 60 ℃ and 120 ℃, and then the thermal stability is respectively verified 1 The 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 with nicotine substances due to the size of the cavity, 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) (( 1 H NMR) comparison plot, wherein (a) nicotine; (b) Nicotine and anion ring-opened cucurbituril clathrate I (molar ratio 1:1); (c) Nicotine and anion ring-opened cucurbituril I clathrate (molar ratio 1:2); (d) anion ring-opened cucurbituril I.
FIG. 2 shows NMR spectra of nornicotine and anion ring-opened cucurbituril II clathrate released at 60 deg.C for different time 1 H NMR) comparison scheme in which (a) nornicotine and anionic cucurbituril II are includedReleasing the substance 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 time 1 H 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.
FIG. 4 is a graph of nicotine release results at 60 ℃;
FIG. 5 is a graph of the results of nicotine release at 120 deg.C;
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 ) n SO 3 Na and n are 3) is dissolved in 25mL of distilled water, the mixture is stirred to be dissolved at the temperature of 20 ℃, 0.16mmol of nicotine is added into the anion ring-opening cucurbituril solution, the mixture is stirred for 7 days at the temperature of 25 ℃, water is removed by decompression and concentration at the temperature of 40 ℃, and the clathrate compound of the anion ring-opening cucurbituril I and the nicotine is prepared by vacuum drying, wherein the yield is 96%.
Example 2
0.154mmol of anionic ring-opened cucurbituril I (R is (CH) 2 ) n SO 3 Na and n are 2) is dissolved in 12mL of distilled water, stirred at 60 ℃ until dissolved, 0.8mmol of nornicotine is added into the anion ring-opening cucurbituril solution, stirred for 6h at 20 ℃, decompressed and concentrated at 20 ℃ to remove water, and vacuum-dried to obtain anion ring-opening cucurbiturilThe clathrate compound of the cyclicauride I and the nornicotine has the yield of 97 percent.
Example 3
0.154mmol of anionic ring-opened cucurbituril I (R is (CH) 2 ) n SO 3 Na and n are 4), dissolving in 40mL of distilled water, stirring at 40 ℃ until the solution is dissolved, adding 0.16mmol of dehydro-demethyl nicotine into the anion ring-opening cucurbituril solution, stirring for 3 days at 60 ℃, performing reduced pressure concentration at 60 ℃ to remove water, and performing vacuum drying to obtain the clathrate compound of the anion ring-opening cucurbituril I and the dehydro-demethyl nicotine, wherein the yield is 95%.
Example 4
0.154mmol of anionic ring-opened cucurbituril I (R is (CH) 2 ) n SO 3 Na 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 ) n SO 3 Na and n are 3) is dissolved in 25mL of distilled water, the mixture is stirred to be dissolved at the temperature of 20 ℃, 0.16mmol of nicotine is added into the anion ring-opening cucurbituril solution, the mixture is stirred for 7 days at the temperature of 25 ℃, water is removed by decompression and concentration at the temperature of 40 ℃, and the clathrate compound of the anion ring-opening cucurbituril II and the nicotine is prepared by vacuum drying, wherein the yield is 99%.
Example 6
0.154mmol of anionic ring-opened cucurbituril II (R is (CH) 2 ) n SO 3 Na 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
Adding 0.154mmol of anion calabashThe arubicide II (R is (CH) 2 ) n SO 3 Na 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 ) n SO 3 Na and n are 4), dissolving in 40mL of distilled water, stirring at 40 ℃ until the solution is dissolved, adding 0.16mmol of methyl neonicotine into the anion ring-opening cucurbituril solution, stirring at 60 ℃ for 3 days, performing reduced pressure concentration at 60 ℃ to remove water, and performing vacuum drying to obtain the inclusion compound of the anion ring-opening cucurbituril II and the methyl neonicotine, wherein the yield is 98%.
Example 9
0.154mmol of anionic ring-opened cucurbituril III (R is (CH) 2 ) n SO 3 Na 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 ) n SO 3 Na and n are 2), dissolving in 12mL of distilled water, stirring at 60 ℃ until dissolving, adding 0.8mmol of denitrified nicotine 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 inclusion compound of anion ring-opening cucurbituril III and denitrified nicotine, wherein the yield is 97%.
Example 11
0.154mmol of anionic ring-opened cucurbituril III (R is (CH) 2 ) n SO 3 Na and N are 3) are dissolved in 6mL of distilled water, stirred at 25 ℃ until the materials are dissolved, 0.16mmol of N-methyl denitrogenated neonicotinoid is added into the solution of anion ring-opening cucurbituril, and stirred at 40 DEG CAnd (3) concentrating under reduced pressure at 40 ℃ for 18 hours 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 ) n SO 3 Na and n are 4) is dissolved in 40mL of distilled water, stirred to be dissolved at 40 ℃, 0.16mmol of 2,3 '-bipyridine is added into the anion ring-opening cucurbituril solution, stirred for 3 days at 60 ℃, decompressed and concentrated at 60 ℃ to remove water, and vacuum drying is carried out to obtain the inclusion compound of the anion ring-opening cucurbituril III and 2,3' -bipyridine, wherein the yield is 95%.
Claims (5)
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 the nicotine substances and the anion ring-opening cucurbituril, and the specific preparation method comprises the following steps: adding anion ring-opened 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 pure water, stopping heating and cooling to room temperature after the solid is completely dissolved, then directly adding nicotine substances into the anion ring-opened 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 the inclusion compound; wherein the feeding molar ratio of the nicotine substance to the anion ring-opening cucurbituril is 1-10;
the structural formula of the nicotine substance is shown as
X is selected from
Said anionic ring-opened cucurbiturils are selected from
Wherein R is (CH) 2 ) n SO 3 Na, where n =2,3 or 4.
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.
3. A clathrate compound produced by the production method described in any one of claims 1 to 2.
4. Use of the clathrate according to claim 3 for application in tobacco.
5. A tobacco product comprising the inclusion compound prepared by the preparation method according to any one of claims 1 to 2.
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