CN113801023A

CN113801023A - A kind of menthol formate latent aroma compound, preparation method and use

Info

Publication number: CN113801023A
Application number: CN202111256158.1A
Authority: CN
Inventors: 朱笛恺; 陶飞燕; 丁玉; 杨柳天壹; 常丹丹; 王益明; 崔韬; 张学建; 吴雷; 潘凌; 郭彦旭; 郭刚; 张艇; 申屠洪钎
Original assignee: China Tobacco Sichuan Industrial Co Ltd
Current assignee: Sichuan University; China Tobacco Sichuan Industrial Co Ltd
Priority date: 2021-10-27
Filing date: 2021-10-27
Publication date: 2021-12-17

Abstract

Dissolving menthol in a sufficient solvent, adding triphosgene, stirring for more than 1min, adding pyridine, stirring and reacting for more than 2h at the temperature of 50-60 ℃, dissolving with the solvent after decompression and concentration, slowly adding into aromatic phenol mixed with a catalyst and stirred for more than 10min, reacting for more than 8h, then spin-drying a reaction system, and finally performing post-treatment, separation and purification to obtain the target menthol formate latent aromatic compound. The latent fragrant compound of the invention has the characteristics of stable property in normal temperature environment and uniform fragrance release under heating condition, can increase and enrich the types of menthol perfumes, broaden the application range of menthol perfume raw materials and aromatic phenol, and can overcome the defects of the menthol and the aromatic phenol, such as: high volatility, small threshold value, heavy fragrance smelling, easy loss in the processing process and the like.

Description

Menthol formate latent fragrant compound, preparation method and application

Technical Field

The invention relates to the technical field of tobacco essence, in particular to a menthol formate latent aroma compound, a preparation method and application thereof.

Background

Menthol, also known as menthol, has a cool mint aroma and a cool taste, is often used for preparing cooling agents for cigarettes, and has the functions of ventilating and refreshing smoke, reducing thorns, reducing impurities and the like. Aromatic phenolic compounds are commonly used tobacco flavors. The vanillin has sweet, bean and milk flavors, has the flavor similar to the characteristic flavor of vanilla beans, has lasting fragrance, can increase the milk sweet flavor, is commonly used for preparing the essence for the cigarettes with the milk fragrance and the sweet flavor, and has the effects of improving the fullness and concentration of smoke, reducing miscellaneous gas and stimulation, and enabling the smoke to be soft and the aftertaste to be clean. The ethyl vanillin has the fragrance similar to vanillin, but has stronger fragrance, the fragrance intensity is 3-4 times of that of the vanillin, the ethyl vanillin presents strong, sweet and vanilla-like smell, and the ethyl vanillin is commonly used for preparing essence for cigarettes with milk fragrance and sweet fragrance, and has the effects of increasing the milk fragrance, improving the richness and smoke concentration of the cigarette fragrance and softening smoke. Maltol has the special taste of caramel cream hard candy, can emit strawberry-like fragrance in a diluted solution, is commonly used for preparing milk fragrance and essence for baking cigarettes, and has the functions of enabling smoke to penetrate, be fluffy and rise, increasing baking sweet fragrance, baking cigarette fragrance and returning the aftertaste to sweet.

However, the four molecules have the characteristics of relatively low volatility and low threshold value, and the direct application of the four molecules in a tobacco formula can bring the defects of volatility and unstable content, and influence the quality stability of tobacco products.

Latent fragrance materials, also known as pro-fragrances, are precursors of fragrances synthesized by physical or chemical means from one or more highly volatile or sublimable fragrances. The flavor precursor has no aroma or unobvious aroma, has weak volatility and stable chemical property at normal temperature, can be stored for a long time, and can release expected flavor components only in the state of burning or heating the tobacco products, thereby achieving the purpose of flavoring the tobacco products. By flavoring the flavor precursor, the loss of the flavor in the processing and storage processes can be reduced while the unique style and characteristics of the tobacco product are endowed, and the flavor precursor plays an important role in reducing the use cost of the flavor and improving the stability of the tobacco product.

Although the problem of loss of mint flavor in mint cigarettes is an original intention of using fragrant substances in the cigarettes, the mint ester compounds synthesized by the prior art have the problems of high volatility, poor stability and the like, so that the field of tobacco essence and flavor still has urgent needs for preparing the mint ester compounds which have stable properties and can uniformly release flavor components.

Disclosure of Invention

The invention aims to solve the problems and provides a menthol formate latent fragrant compound, a preparation method and application thereof. Meanwhile, the aromatic substances such as menthol and aromatic phenol can be cracked and released at high temperature (under the smoking condition), so that the smoking quality of the cigarette is improved, and the style of the cigarette is revealed.

The invention realizes the purpose through the following technical scheme:

a menthol formate latent fragrant compound has the following structural formula:

wherein R has the following structure:

the invention also provides a preparation method of the menthol formate latent fragrant compound, which has the following preparation reaction formula:

the preparation method comprises the following steps: dissolving menthol in a sufficient amount of solvent, adding triphosgene, stirring for more than 1min, adding pyridine, stirring and reacting at 50-60 ℃ for more than 2h, concentrating under reduced pressure, dissolving with the solvent, slowly adding into aromatic phenol mixed with a catalyst and stirred for more than 10min, reacting for more than 8h, then spin-drying the reaction system, and finally performing post-treatment, separation and purification to obtain the target latent aromatic compound. The first stirring time is more than 1min, preferably 1-10 min; the time of the second stirring is more than 2 hours, preferably 2-6 hours, and the actual stirring time is determined according to the reaction condition; the time for the third stirring is more than 10min, preferably 10-60 min.

The further scheme is that the solvent is one or more of diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, methyl tetrahydrofuran, dichloromethane, 1, 2-dichloroethane, dimethyl sulfoxide and petroleum ether.

In a further scheme, the aromatic phenol is one or more of vanillin, ethyl vanillin or maltol.

In the further scheme, the catalyst is triethylamine.

The further scheme is that the molar ratio of the menthol to the triphosgene to the pyridine to the aromatic phenol is 5 (2-3) to 5-6 to 4-4.5.

Further, the post-treatment is that water and ethyl acetate are added, an organic phase is retained, water is used for washing twice, and the obtained residue is treated by petroleum ether: and (3) performing column chromatography separation on ethyl acetate which is 20:1-15: 1.

The invention also provides the use of the latent fragrant compound and the latent fragrant compound prepared by the preparation method as spices, and particularly the latent fragrant compound is added into products which release fragrance during combustion or heating according to the addition ratio of 0.00001-10% by weight, such as incense for producing specific fragrance, candle or fireplace fuel, or seasoning juice, halogen materials or vegetable oil with special flavor, or other substances which release flavor during combustion or heating, such as tobacco.

The invention also provides the latent aroma compound and the application of the latent aroma compound prepared by the preparation method in tobacco, and specifically the latent aroma compound is added into the tobacco according to the addition proportion of 0.00001-2% of the weight of the tobacco.

The further proposal is that the adding method of the latent-fragrance compound into the tobacco is surface fragrance adding, fragrance adding or sheet fragrance adding; or dissolving the latent fragrant compound in water, alcohol or their mixture, and spraying or injecting the solution onto tobacco; the tobacco is a blended or cured tobacco type finished product, or is a component of a finished product formulation.

The invention has the beneficial effects that:

the latent fragrant compound of the invention has the characteristics of stable property in normal temperature environment and uniform fragrance release under heating condition, can increase and enrich the types of menthol perfumes, broaden the application range of menthol perfume raw materials and aromatic phenol, and can overcome the defects of the menthol and the aromatic phenol, such as: high volatility, small threshold value, heavy fragrance smelling, easy loss in the processing process and the like.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the embodiments or the drawings needed to be practical in the prior art description, and obviously, the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 is a 1H NMR nuclear magnetic spectrum of latent aromatic compound LY1 of the present invention.

FIG. 2 is a 13C NMR nuclear magnetic spectrum of latent aromatic compound LY1 of the present invention.

FIG. 3 is an ESI-MS mass spectrum of latent aromatic compound LY1 of the present invention.

FIG. 4 is a 1H NMR nuclear magnetic spectrum of latent aromatic compound LY2 of the present invention.

FIG. 5 is a 13C NMR nuclear magnetic spectrum of latent aromatic compound LY2 of the present invention.

FIG. 6 is an ESI-MS mass spectrum of latent aromatic compound LY2 of the present invention.

FIG. 7 is a 1H NMR nuclear magnetic spectrum of latent aromatic compound LY4 of the present invention.

FIG. 8 is a 13C NMR nuclear magnetic spectrum of latent aromatic compound LY4 of the present invention.

FIG. 9 is an ESI-MS mass spectrum of latent aromatic compound LY4 of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.

Example 1

Menthol (0.75g, 4.81mmol) was dissolved in (anhydrous) dichloromethane (10ml), triphosgene (0.58g, 1.77mmol, anhydrous dichloromethane dissolved) was added and stirred, and then pyridine (0.4ml, 4.91mmol) was added dropwise. Stirring at 50-60 deg.C for 5h, concentrating under reduced pressure to dryness (about 1.75g, about 4.8mmol of rotary dry solid), adding dichloromethane to dissolve, adding catalytic amount of triethylamine into 4mmol of vanillin, stirring for about 20min, slowly adding dropwise into the above solution, reacting overnight, and TLC point plate almost completely reacting. The reaction was spin dried, water and ethyl acetate were added, the organic phase was retained and washed twice with water. Using petroleum ether: column chromatography with ethyl acetate (20: 1-15: 1) gave the product LY1 in 78% yield.

The results of the tests are shown in FIGS. 1-3, where the structures are characterized as follows:

¹HNMR(400MHz,CDCl₃):δ,ppm 0.85(d,3H),0.95(d,6H),1.03～1.29(m,3H),1.46～1.53(m,2H),1.66～1.76(m,2H),2.01～2.09(m,4H),3.92(s,3H),4.60～4.67(m,1H),7.31～7.33(m,1H),7.47～7.51(m,2H)，9.95(s,1H)；¹³CNMR(100MHz,CDCl₃):δ,ppm 191.0,152.2,152.0,145.3,135.2,124.8,122.8,110.8,80.1,56.1,47.0,40.5,34.0,31.4,26.2,23.4,22.0,20.7,16.4；ESI-MS(m/z):357.1663[M+Na]⁺.

example 2

Menthol (0.75g, 4.81mmol) was dissolved in (anhydrous) dichloromethane (10ml), triphosgene (0.58g, 1.77mmol, anhydrous dichloromethane dissolved) was added and stirred, and then pyridine (0.4ml, 4.91mmol) was added dropwise. Stirring at 50-60 deg.C for 5h, concentrating under reduced pressure to dryness (about 1.75g, about 4.8mmol of rotary dry solid), adding dichloromethane to dissolve, adding catalytic amount of triethylamine into ethyl vanillin 4mmol, stirring for about 20min, slowly adding dropwise into the above solution, and reacting overnight. The reaction was spin dried, water and ethyl acetate were added, the organic phase was retained and washed twice with water. Using petroleum ether: column chromatography with ethyl acetate 20:1-15:1 gave LY2 in 76% yield.

The test results are shown in FIGS. 4-6, where the structures are characterized as follows:

¹HNMR(400MHz,CDCl₃):δ,ppm 0.85(d,3H),0.95(d,6H),1.03～1.26(m,3H),1.42～1.46(m,3H),1.43(t,3H),1.48～1.54(m,4H),1.57(s,1H),1.70～1.74(m,2H),2.05～2.10(m,1H),2.10～2.19(m,2H)，4.15(q,2H),4.59～4.65(m,1H),7.31～7.33(m,1H),7.45～7.48(m,2H)，9.94(s,1H)；¹³CNMR(100MHz,CDCl₃):δ,ppm 191.1,152.1,151.5,145.3,135.2,124.5,122.9,111.7,79.9,64.7,47.0,40.5,34.0,31.4,26.2,23.5,22.0,20.7,16.5,14.5；ESI-MS(m/z):371.1816[M+Na]⁺.

example 3

Menthol (0.75g, 4.81mmol) was dissolved in (anhydrous) dichloromethane (10ml), triphosgene (0.58g, 1.77mmol, anhydrous dichloromethane dissolved) was added and stirred, and then pyridine (0.4ml, 4.91mmol) was added dropwise. Stirring at 50-60 deg.C for 5h, concentrating under reduced pressure to dryness (about 1.75g, about 4.8mmol of rotary dried solid), adding dichloromethane to dissolve, adding catalytic amount of triethylamine into 4mmol of maltol, stirring for about 20min, slowly adding dropwise into the above solution, and reacting overnight. The reaction was spin dried, water and ethyl acetate were added, the organic phase was retained and washed twice with water. Using petroleum ether: column chromatography with ethyl acetate (20: 1-15: 1) gave the product LY4 in 72% yield.

The results of the tests are shown in FIGS. 7-9, where the structures are characterized as follows:

¹HNMR(400MHz,CDCl₃):δ,ppm 0.85(d,3H),0.94(d,6H),1.02～1.21(m,2H),1.46～1.54(m,2H),1.68～1.73(m,2H),2.03～2.10(m,1H),2.14～2.20(m,1H),2.31(s,1H),4.59～4.65(m,1H),6.41(d,1H),6.68(d,1H)；¹³CNMR(100MHz,CDCl₃):δ,ppm 171.9,159.0,154.2,151.7,139.1,116.9,80.5,47.0,40.4,34.0,31.4,26.3,23.5,21.9,20.6,16.4,14.8；ESI-MS(m/z):331.1503[M+Na]⁺.

example 4

LY4 cigarette flavoring evaluation test is used to show that the compound improves the cigarette smoke aroma. Weighing a certain amount of LY4, dissolving with ethanol, adding 0.003% of the solution to certain tobacco type tobacco shreds of a flue-cured tobacco, and rolling into experimental cigarettes. And (4) adding the same proportion of ethanol into the same cut tobacco to roll the cut tobacco into blank cigarettes. The comparison and the smoking evaluation show that compared with a control sample, the experimental cigarette has more obvious sweet aroma, herb aroma and baking aroma and has the effects of reducing thorns and removing impurities.

In conclusion, the invention discloses the preparation of the latent fragrant compound (LY) and the application thereof in cigarette flavoring, the novel latent fragrant compound can uniformly release menthol and aromatic phenol to the smoke of the cigarette when the cigarette is burnt, and the latent fragrant compound has the advantages of high boiling point, low volatility, light fragrance smelling and the like, and has good smoke flavoring effect when being used for flavoring the cigarette. The target latent aroma compound added into the cigarette releases corresponding specific aroma in the cigarette, and simultaneously overcomes the defects of high volatility, small threshold value, heavy aroma smelling, easy loss in the processing process and the like of the menthol and the aromatic phenol.

The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims. It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. a latent fragrance compound of menthol formate, its general structural formula is as follows:

where R has the following structure:

2. the preparation method of a kind of menthol formate latent fragrance compound as claimed in claim 1, is characterized in that, preparation reaction formula is as follows:

The specific preparation method is as follows: dissolving menthol in a sufficient amount of solvent, adding triphosgene and stirring for more than 1 min, adding pyridine, stirring and reacting at 50-60 ° C for more than 2 h, concentrating under reduced pressure and dissolving with solvent, then slowly adding to Mix and stir with the catalyst in the aromatic phenol for more than 10 minutes, react for more than 8 hours, then spin the reaction system to dry, and finally carry out post-processing, separation and purification to obtain the target latent aroma compound.

3. the preparation method of a kind of menthol formate latent fragrance compound as claimed in claim 2, is characterized in that, described solvent is ether, methyl tertiary butyl ether, tetrahydrofuran, dioxane, methyl tetrahydrofuran , one or more of dichloromethane, 1,2-dichloroethane, dimethyl sulfoxide and petroleum ether.

4. the preparation method of a kind of menthol formate latent fragrance compound as claimed in claim 2, is characterized in that, described aromatic phenol is one or more in vanillin, ethyl vanillin or maltol kind.

5. the preparation method of a kind of menthol formate latent fragrance compound as claimed in claim 2, is characterized in that, described catalyzer is triethylamine.

6. the preparation method of a kind of menthol formate latent fragrance compound as claimed in claim 2, is characterized in that, the mol ratio of described menthol, triphosgene, pyridine and aromatic phenol is 5:(2～3) :(5～6):(4～4.5).

7. the preparation method of a kind of menthol formate latent fragrance compound as claimed in claim 2, is characterized in that, described aftertreatment refers to adding water and ethyl acetate, retains organic phase, uses washing twice, obtains The residue was separated by column chromatography with petroleum ether:ethyl acetate=20:1-15:1.

8. The latent fragrance compound as claimed in claim 1 and the latent fragrance compound prepared by the preparation method described in 2-7 are used as the purposes of the fragrance, specifically for adding the latent fragrance compound to the combustion according to the weight 0.00001%～10% addition ratio. Or in products that release fragrance during heating.

9. the latent fragrance compound as claimed in claim 1, the purposes of the latent fragrance compound prepared by the preparation method described in 2-7 in tobacco, specifically is adding latent fragrance compound with the addition ratio of tobacco weight 0.00001%～2% into tobacco.

10. the use method of latent fragrance compound according to claim 9, it is characterized in that the adding method that described latent fragrance compound is added in tobacco is adding surface fragrance, adding fragrance or flake fragrance; Or the latent fragrance compound is dissolved in water, alcohol or a mixed solvent of the two, and then spraying or injecting the solution onto the tobacco; the tobacco is a mixed or flue-cured finished product, or a component of the finished product formulation.