阅读说明：本技术 一种芳香酚酯潜香化合物、制备方法及用途 (Aromatic phenolic ester latent aromatic compound, preparation method and application ) 是由 陶飞燕 朱笛恺 丁玉 崔韬 邓发达 杨柳天壹 常丹丹 王益明 杨涓 张学建 丁为 于 2021-10-27 设计创作，主要内容包括：本发明公开了一种芳香酚酯潜香化合物、制备方法及用途,将芳香酚与催化剂在-10℃～10℃温度条件下搅拌溶解于足量溶剂中,缓慢滴入溶解在足量溶剂中的酰氯,在0℃～50℃温度条件下搅拌6h以上,最后进行后处理分离纯化得到目标芳香酚酯潜香化合物。本发明的潜香化合物具有常温环境下性质稳定,在加热条件下能够均匀释放芳香酚及酸类化合物香味的特性,同时还可增加和丰富芳香酚香料的种类、拓宽芳香酚香原料及酰氯的应用范围,还可克服芳香酚及酰氯自身的缺陷,如：挥发性高、阈值小、闻香重、加工过程易损失等。(The invention discloses an aromatic phenolic ester latent aromatic compound, a preparation method and application thereof, aromatic phenol and a catalyst are stirred and dissolved in a sufficient amount of solvent at the temperature of-10 ℃, acyl chloride dissolved in the sufficient amount of solvent is slowly dropped, the aromatic phenolic ester latent aromatic compound is stirred for more than 6 hours at the temperature of 0-50 ℃, and finally, the target aromatic phenolic ester latent aromatic compound is obtained by post-treatment, separation and purification. The latent fragrant compound of the invention has the characteristics of stable property in normal temperature environment and uniform fragrance release of aromatic phenol and acid compounds under heating condition, can increase and enrich the variety of aromatic phenol perfumes, broaden the application range of aromatic phenol perfume raw materials and acyl chloride, and can overcome the defects of aromatic phenol and acyl chloride, such as: high volatility, small threshold value, heavy fragrance smelling, easy loss in the processing process and the like.)

1. An aromatic phenolic ester latent aromatic compound, which has the following structural formula:

R₁-O-R₂；

wherein R is₁Has the following structure:

wherein R is₂Has the following structure:

2. the process for producing an aromatic phenol ester latent aromatic compound according to claim 1, wherein the reaction formula is as follows:

R₁-OH+R₂-Cl→R₁-O-R₂；

the specific operation method comprises the following steps: stirring and dissolving aromatic phenol and a catalyst in a sufficient amount of solvent at the temperature of-10 ℃, slowly dripping acyl chloride dissolved in the sufficient amount of solvent, stirring for more than 6 hours at the temperature of 0-50 ℃, and finally performing post-treatment, separation and purification to obtain the target aromatic phenol ester latent aromatic compound.

3. The method of claim 2, wherein the solvent is one or more of ethyl ether, methyl t-butyl ether, tetrahydrofuran, dioxane, methyl tetrahydrofuran, dichloromethane, 1, 2-dichloroethane, dimethyl sulfoxide, and petroleum ether.

4. The method of claim 2, wherein the aromatic phenol is one or more of vanillin, ethyl vanillin, maltol or eugenol.

5. The process for producing an aromatic phenol ester latent aromatic compound according to claim 2, wherein the catalyst is triethylamine; the acyl chloride is one or more of dodecanoyl chloride, tetradecanoyl chloride or oleoyl chloride.

6. The method for preparing the latent aromatic compound of an aromatic phenolic ester according to claim 2, wherein the molar ratio of the aromatic phenolic acid chloride is 1 (1-1.5).

7. The process for the preparation of the latent aromatic compound of aromatic phenol ester according to claim 2, wherein the post-treatment comprises adding methylene chloride, washing three times with dilute hydrochloric acid, washing one time with saturated brine, removing the solvent by vacuum concentration, and removing the residue by washing with petroleum ether: and (3) performing column chromatography separation on ethyl acetate which is 20:1-15: 1.

8. The latent fragrant compound according to claim 1 or the latent fragrant compound prepared by the preparation method according to 2 to 7, wherein the latent fragrant compound is added into a product which releases fragrance during burning or heating according to an addition ratio of 0.00001 to 10 percent by weight.

9. The latent aroma compound according to claim 1 and the use of the latent aroma compound prepared by the preparation method of 2 to 7 in tobacco, specifically, the latent aroma compound is added to the tobacco at an addition ratio of 0.00001 to 2 percent of the weight of the tobacco.

10. Method of use of an pro-fragrance compound according to claim 9, characterized in that the pro-fragrance compound is added to tobacco by a method of top-note, top-note or sheet flavoring; 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.

Technical Field

The invention relates to the technical field of tobacco essence, in particular to an aromatic phenolic ester latent aroma compound, a preparation method and application thereof.

Background

Aromatic phenol compounds are widely used in 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. Eugenol has mild spicy and sweet fragrance, sweet clove fragrance and strong and lasting fragrance, is commonly used for preparing the spicy and sweet fragrance essence for cigarettes, and has the effects of increasing the smoke volume and concentration, softening smoke and roasting the smoke fragrance. Maltol, also known as methyl 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 effects of enabling smoke to be transparent, fluffy and upwelling, increasing baking sweet fragrance, baking smoke fragrance and returning the aftertaste to sweet. Although the acyl chloride compound is not usually directly used for blending tobacco essence, the aromatic phenolic ester synthesized by the acyl chloride compound and aromatic phenol can release acid compounds under high-temperature cracking, can play a role in neutralizing nicotine, and has the effects of reducing thorn, removing impurities, softening smoke and the like.

However, the molecules have the characteristics of high volatility and low threshold value, and the direct application of the molecules in a tobacco formula can bring the defects of high volatility and unstable content, thereby influencing 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.

Disclosure of Invention

The invention aims to solve the problems and provides an aromatic phenol ester latent aromatic compound, a preparation method and application. Meanwhile, aromatic phenol, acid compounds and other fragrant substances can be cracked and released at high temperature (under the smoking condition), so that the smoking quality of the cigarettes is improved, and the style of the cigarettes is revealed.

The invention realizes the purpose through the following technical scheme:

an aromatic phenolic ester latent aromatic compound, which has the following structural formula:

R₁-O-R₂；

wherein R is₁Has the following structure:

wherein R is₂Has the following structure:

the invention also provides a preparation method of the aromatic phenolic ester latent aromatic compound, which comprises the following steps:

R₁-OH+R₂-Cl→R₁-O-R₂

the specific operation method comprises the following steps: stirring and dissolving aromatic phenol and a catalyst in a sufficient amount of solvent at the temperature of-10 ℃, slowly dripping acyl chloride dissolved in the sufficient amount of solvent, stirring for more than 6 hours at the temperature of 0-50 ℃, and finally performing post-treatment, separation and purification to obtain the target aromatic phenol ester latent aromatic compound.

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, maltol or eugenol.

In the further scheme, the catalyst is triethylamine; the acyl chloride is one or more of dodecanoyl chloride, tetradecanoyl chloride or oleoyl chloride.

In a further scheme, the molar ratio of the aromatic phenolic acyl chloride is 1 (1-1.5).

Further, the post-treatment is carried out by adding dichloromethane, washing with dilute hydrochloric acid for three times, washing with saturated common salt water for one time, vacuum-concentrating to remove the solvent, and reacting the obtained residue with petroleum ether: and (3) performing column chromatography separation on ethyl acetate which is 20:1-15: 1.

The reaction temperature in the preparation method is preferably 10-30 ℃. The time for the first stirring is more than 10min, preferably 10-30 min. The second stirring time is more than 6 hours, preferably 6 to 10 hours.

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 of aromatic phenol and acid compounds under heating condition, can increase and enrich the variety of aromatic phenol perfumes, broaden the application range of aromatic phenol perfume raw materials and acyl chloride, and can overcome the defects of aromatic phenol and acyl chloride, 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 LSD8 of the present invention.

FIG. 2 is a 13C NMR nuclear magnetic spectrum of latent aromatic compound LSD8 of the present invention.

FIG. 3 is an ESI-MS mass spectrum of latent aromatic compound LSD8 of the present invention.

FIG. 4 is a 1H NMR nuclear magnetic spectrum of latent aromatic compound LSD13 of the present invention.

FIG. 5 is a 13C NMR nuclear magnetic spectrum of latent aromatic compound LSD13 of the present invention.

FIG. 6 is an ESI-MS mass spectrum of latent aromatic compound LSD13 of the present invention.

FIG. 7 is a 1H NMR nuclear magnetic spectrum of latent aromatic compound LSD18 of the present invention.

FIG. 8 is a 13C NMR nuclear magnetic spectrum of latent aromatic compound LSD18 of the present invention.

FIG. 9 is an ESI-MS mass spectrum of latent aromatic compound LSD18 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

Adding 15ml of dichloromethane and 0.8ml of triethylamine into 5mmol of vanillin, and stirring for 10 minutes in ice bath; 5mmol of acid chloride is dissolved in 5ml of dichloromethane, slowly added dropwise to the vanillin solution and stirred for 8h at 25 ℃. The reaction product was washed with 200ml dichloromethane three times with 50ml each time 1M dilute hydrochloric acid and then once with 50ml saturated brine, concentrated in vacuo to remove the solvent and concentrated with petroleum ether: column chromatography with ethyl acetate 20:1-15:1 gave the product LSD8 in 76% yield.

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

LSD-08:1HNMR(400MHz,CDCl3):δ,ppm 0.88(t,3H),1.26～1.43(m,16H),1.73～1.80(m,2H),2.6(t,2H),3.89(s,3H),7.21(d,1H),7.46～7.49(m,2H),9.95(s,1H)；13CNMR(100MHz,CDCl3):δ,ppm 191.1,171.2,152.0,145.1,135.1,124.8,123.4,110.8,56.0,34.0,31.9,29.6,29.5,29.3,29.0,24.9,22.7；ESI-MS(m/z):357.2024[M+Na]+

example 2

Adding 15ml of dichloromethane and 0.8ml of triethylamine into 5mmol of ethyl vanillin, and stirring for 10 minutes in ice bath; 5mmol tetradecanoyl chloride is dissolved in 5ml dichloromethane, slowly added dropwise to the vanillin solution, and stirred at 25 ℃ for 8 h. The reaction product was washed with 200ml dichloromethane three times with 50ml each time 1M dilute hydrochloric acid and then once with 50ml saturated brine, concentrated in vacuo to remove the solvent and concentrated with petroleum ether: column chromatography with ethyl acetate 20:1-15:1 gave product LSD13 in 89% yield.

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

LSD-13:1HNMR(400MHz,CDCl3):δ,ppm 0.88(t,3H),1.26～1.36(m,18H),1.40～1.46(m,5H),1.74～1.81(m,2H),2.59(t,2H),4.13(dd,2H),7.20(d,1H),7.44～7.47(m,2H),9.93(s,1H)；13CNMR(100MHz,CDCl3):δ,ppm 191.1,171.2,151.4,145.3,135.1,124.6,123.4,111.7,64.9,34.0,31.9,29.7,29.7,29.6,29.5,29.4,29.3,29.1,25.0,22.7,14.6,14.1；ESI-MS(m/z):399.2492[M+Na]+

example 3

Adding 15ml of dichloromethane and 0.8ml of triethylamine into 5mmol of maltol, and stirring for 10 minutes in ice bath; 5mmol oleoyl chloride was dissolved in 5ml dichloromethane and slowly added dropwise to the vanillin solution and stirred at 25 ℃ for 8 h. The reaction product was washed with 200ml dichloromethane three times with 50ml each time 1M dilute hydrochloric acid and then once with 50ml saturated brine, concentrated in vacuo to remove the solvent and concentrated with petroleum ether: column chromatography with ethyl acetate 20:1-15:1 gave LSD18 in 82% yield.

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

LSD-18:1HNMR(400MHz,CDCl3):δ,ppm 0.88(t,3H),1.23～1.43(m,20H),1.72～1.77(m,2H),1.96～2.06(m,5H),2.25(s,3H),2.60(t,2H),4.12(q,1H),5.33～5.38(m,2H),6.39(d,2H),7.67(d,1H)；13CNMR(100MHz,CDCl3):δ,ppm 172.2,170.5,159.1,154.1,138.7,130.0,129.7,116.8,33.6,31.9,29.8,29.7,29.5,29.3,29.2,29.1,29.0,27.2,27.2,24.8,22.7,15.0,14.1；ESI-MS(m/z):399.2492[M+Na]+

example 4

LSD8 cigarette flavoring and smoking evaluation experiments are used for explaining that the compounds improve the cigarette smoke aroma. Weighing a certain amount of LSD8, dissolving with ethanol, adding 0.003% of LSD8 into certain tobacco type of flue-cured tobacco, and making into experimental cigarette. 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 the control sample, the experimental cigarette has more obvious sweet aroma, milk aroma and bean aroma, and has the effects of softening smoke and reducing thorn.

In conclusion, the invention discloses the preparation of a latent aroma compound (LSD) and the application thereof in cigarette flavoring, the novel latent aroma compound can uniformly release aromatic phenol and acid compounds to cigarette smoke when the cigarette is burnt, and the latent aroma compound has the advantages of high boiling point, low volatility, light aroma smelling and the like, and has good smoke aroma-enhancing effect when being used for cigarette flavoring. 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 aromatic phenol and acyl chloride.

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.