阅读说明：本技术 一种肉桂醇降龙涎碳酸酯潜香物及其制备方法和应用 (Cinnamyl alcohol ambroxol carbonate latent aroma, and preparation method and application thereof ) 是由 陶飞燕 丁玉 吴雷 常丹丹 朱笛恺 杨柳天壹 杨涓 崔韬 罗诚 周志刚 潘凌 于 2021-08-05 设计创作，主要内容包括：本发明公开了一种肉桂醇降龙涎碳酸酯潜香物及其制备方法和应用,将肉桂醇与1,1’-羰基二咪唑溶于干燥的四氢呋喃中,加热搅拌反应；TLC跟踪反应终点,反应完成后,向有机相中加入二氯甲烷和去离子水,分液,有机相用无水硫酸镁除水,浓缩,得液体A；取降龙涎二醇和N,N-二甲基甲酰胺加入液体A中,加热搅拌反应,反应后降至室温；向有机相中加去离子水和二氯甲烷,分液,有机相依次用去离子水、饱和NaCl溶液洗涤,有机相用无水硫酸镁除水,浓缩得到油状液体,然后柱层析分离纯化,得到肉桂醇降龙涎碳酸酯潜香物。本发明为高挥发性、阈值较小的香料小分子的应用提供了很好的典范,可增加和丰富龙涎香韵及拓宽龙涎香香原料及肉桂醇的应用范围。(The invention discloses a cinnamyl alcohol ambroxol carbonate latent aromatic, a preparation method and application thereof, wherein cinnamyl alcohol and 1, 1' -carbonyl diimidazole are dissolved in dry tetrahydrofuran and are heated and stirred for reaction; tracking the reaction end point by TLC, after the reaction is finished, adding dichloromethane and deionized water into the organic phase, separating liquid, removing water from the organic phase by using anhydrous magnesium sulfate, and concentrating to obtain liquid A; adding ambroxol and N, N-dimethylformamide into the liquid A, heating and stirring for reaction, and cooling to room temperature after reaction; adding deionized water and dichloromethane into the organic phase, separating the liquid, washing the organic phase with deionized water and saturated NaCl solution successively, dewatering the organic phase with anhydrous magnesium sulfate, concentrating to obtain oily liquid, and separating and purifying by column chromatography to obtain cinnamyl alcohol ambergris carbonate latent aroma. The invention provides a good model for the application of perfume micromolecules with high volatility and smaller threshold value, can increase and enrich ambergris scent and broaden the application range of ambergris scent raw materials and cinnamyl alcohol.)

1. The cinnamyl alcohol ambroxol carbonate latent aromatic is characterized by having a structural formula as follows:

2. a process for the preparation of cinnamyl alcohol norambrox carbonate latently as claimed in claim 1, characterized in that it comprises the following steps:

the method comprises the following steps: dissolving cinnamyl alcohol and 1, 1' -carbonyl diimidazole in dry tetrahydrofuran, and heating and stirring for reaction; monitoring cinnamyl alcohol and a reaction product of cinnamyl alcohol and 1, 1' -carbonyldiimidazole by TLC, tracking the reaction end point, adding dichloromethane and deionized water into an organic phase after the reaction is finished, separating liquid, removing water from the organic phase by using anhydrous magnesium sulfate, and concentrating to obtain liquid A;

step two: adding ambroxol and N, N-dimethylformamide into the liquid A, heating and stirring for reaction, and cooling to room temperature after reaction; adding deionized water and dichloromethane into the organic phase, separating the liquid, washing the organic phase with deionized water and saturated NaCl solution successively, dewatering the organic phase with anhydrous magnesium sulfate, concentrating to obtain oily liquid, and separating and purifying by column chromatography to obtain cinnamyl alcohol ambergris carbonate latent aroma.

3. The method of claim 2, wherein the molar ratio of cinnamyl alcohol, 1' -carbonyldiimidazole and ambroxol is 1 (1.5-3) to (1-1.5).

4. The method for preparing cinnamyl alcohol norambrox carbonate latently fragrant substance according to claim 2, characterized in that the heating and stirring reaction in the step one is a reaction at 15-40 ℃ for 1-6 h.

5. The method for preparing cinnamyl alcohol norambrox carbonate latently fragrant substance according to claim 2, characterized in that the heating and stirring reaction in the second step is a reaction at 30-120 ℃ for 1-12 h.

6. The use of cinnamyl alcohol norambrox carbonate latexes of claim 1, wherein cinnamyl alcohol norambrox carbonate latexes are added to tobacco at an add rate of 0.00001% to 2% by weight of tobacco.

7. The use of the cinnamyl alcohol norambroxate ester latent fragrance of claim 6, wherein the cinnamyl alcohol norambroxate ester latent fragrance is added to tobacco by adding top notes, flavoring notes or sheet flavoring, wherein the tobacco is a blended or flue-cured type cigarette product, or is a novel tobacco product.

Technical Field

The invention relates to the field of tobacco flavors, in particular to an ambergris flavor and taste-improving latent flavor based on ester bond connection of ambergris glycol and cinnamyl alcohol and application thereof in cigarette flavoring.

Background

Ambergris is a very popular blending perfume in the market, and is called four big animal perfumes together with musk, civet and marigold. Ambrox is a precious ambergris raw material, has strong and special ambergris fragrance, is called the fragrance of ambergris by the unique fragrance fixing ability, is described as the mild ambergris fragrance as delicate velvet, has ambergris effect, is the fragrance of ambergris, is an excellent fragrance fixing agent, and is the highest one of all synthetic ambergris fragrances. Has been used as a substitute of natural ambergris, is used in high-grade perfume and cosmetic essence, and is very suitable for perfuming skin, hair and fabrics because of no irritation to human body and no allergic reaction to animals.

Ambrox exists in Turkish tobacco, is a product of degradation of Labdane substances, gives sweet aroma, flower aroma and costustoot aroma to cigarette smoke, can cover up crude miscellaneous gas of tobacco, gives pleasant characteristic aroma to the tobacco, makes the cigarette soft and mellow, leaves long aftertaste, is an effective aroma-enhancing and flavoring agent, and is tuned and combined with the costustoot with the characteristics of the tobacco.

However, ambrox has small molecular weight, high volatility, heavy smell and low threshold. The loss is easy in the cigarette processing process, the fragrance is not uniformly released in the cigarette smoking process, and the quality of the cigarettes is unstable due to the volatilization and the loss of the flavoring agent during the storage period.

The cinnamyl alcohol exists in certain natural products in an ester or free state, such as cinnamon leaves, hyacinth, clematis-shaped aristolochia debilis, halbereaf yellowhorn, taffodil, benzoin, storax, Peru balsam and the like, has mild and comfortable pleasant fragrance resin smell similar to hyacinth, has elegant fragrance, is an indispensable spice for preparing narcissus essence, rose essence and the like, and is a spice widely applied in daily essences. The essence is also used for tobacco, is used for blending spicy and nut flavors in the tobacco essence, can enrich the tobacco flavor, improve the smoking taste, is soft but not lasting, is easy to volatilize in the processing and storage processes, loses the characteristic aroma of the tobacco and cannot be well applied to the tobacco formula.

The precursor of the flavoring agent is synthesized by a physical or chemical means, has no or little flavor at normal temperature, and is pyrolyzed into one or more molecular fragments under the smoking state of the cigarette to release the flavoring agent, thereby playing the role of improving the quality of the mainstream smoke of the cigarette and achieving the aim of flavoring. The fragrance precursor compound can endow the cigarette with a characteristic style, and fragrance components can be slowly released in the smoking process of the cigarette, so that the fragrance is improved, and the quality of the cigarette is further improved. Meanwhile, the amount of the essence can be reduced, the stability and the storage property of the essence are improved, and the perfuming process is simple and convenient. And the influence on the taste of the cigarettes caused by other factors in the processing process is also avoided.

Disclosure of Invention

The invention overcomes the defects of the prior art and provides a preparation method of a carbonate latent aroma with ambergris aroma and improved smoking taste based on ester bond connection of ambergris diol and cinnamyl alcohol and application of the carbonate latent aroma in cigarette flavoring.

The invention adopts the following technical scheme:

a cinnamyl alcohol norambrox carbonate latent aroma with ambergris aroma and improved taste, the structural formula of which is as follows:

the latent perfume has the characteristics of high stability and strong processing resistance, and can overcome the defects of volatility, small threshold value, nonuniform release, easy loss in the processing process and the like of ambergris ether and cinnamyl alcohol. Meanwhile, the cinnamyl alcohol can be cracked and released at high temperature (under the condition of smoking) and the ambroxol ester can be cyclized to generate ambroxol ether fragrance substances, so that the smoking quality of cigarettes is improved, and the style of the cigarettes is revealed.

The preparation method of the cinnamyl alcohol ambroxol carbonate latent aromatic comprises the following steps:

the method comprises the following steps: dissolving cinnamyl alcohol and 1, 1' -carbonyl diimidazole in dry tetrahydrofuran, and heating and stirring for reaction; monitoring cinnamyl alcohol and a reaction product of cinnamyl alcohol and 1, 1' -carbonyldiimidazole by TLC, tracking the reaction end point, adding dichloromethane and deionized water into an organic phase after the reaction is finished, separating liquid, removing water from the organic phase by using anhydrous magnesium sulfate, and concentrating to obtain liquid A;

step two: adding ambroxol and N, N-dimethylformamide into the liquid A, heating and stirring for reaction, and cooling to room temperature after reaction; adding deionized water and dichloromethane into the organic phase, separating the liquid, washing the organic phase with deionized water and saturated NaCl solution successively, dewatering the organic phase with anhydrous magnesium sulfate, concentrating to obtain oily liquid, and separating and purifying by column chromatography to obtain cinnamyl alcohol ambergris carbonate latent aroma.

The mol ratio of the cinnamyl alcohol, the 1, 1' -carbonyl diimidazole and the ambroxol is 1 (1.5-3) to 1-1.5.

The heating stirring reaction in the step one refers to a reaction at 15-40 ℃ for 1-6 h.

The heating stirring reaction in the second step means reaction at 30-120 ℃ for 1-12 h.

The application method of the cinnamyl alcohol ambrox carbonate latent aroma comprises the step of adding the cinnamyl alcohol ambrox carbonate latent aroma into tobacco according to the adding proportion of 0.00001-2% of the weight of the tobacco.

The cinnamyl alcohol ambrox ester latent aroma is added into tobacco by adding surface aroma, adding material aroma or adding aroma to sheets, and the tobacco is a mixed type or flue-cured tobacco type cigarette product or a novel tobacco product.

Compared with the prior art, the invention has at least the following beneficial effects:

compared with the traditional carbonic acid diester preparation method, the preparation method has the advantages of low cost, simple and convenient operation and the like. The preparation and the application of the latent aroma compound provide a good model for the application of perfume micromolecules with high volatility and smaller threshold, and simultaneously can increase and enrich ambergris aroma, improve the taste, widen the application range of ambergris aroma raw materials and cinnamyl alcohol, and overcome the defects of ambergris ether and cinnamyl alcohol, such as: small molecular weight, easy volatilization, small threshold, uneven release, easy loss in the processing process and the like.

Drawings

FIG. 1 is a drawing of cinnamyl alcohol norambroxate ester latently fragrant¹H NMR spectrum.

FIG. 2 is cinnamyl alcohol norambroxol carbonateOf latent fragrances¹³C NMR spectrum.

FIG. 3 is an IR spectrum of a cinnamyl alcohol norambroxate latent fragrance.

Figure 4 is a HRMS spectrum of a cinnamyl alcohol norambroxate latent fragrance.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Example 1

1mmol of cinnamyl alcohol and 3mmol of 1, 1' -carbonyldiimidazole are dissolved in 20mL of dry tetrahydrofuran and heated to 23 ℃ for stirring reaction for 3 h. TLC is used for monitoring cinnamyl alcohol and reaction products of cinnamyl alcohol and 1, 1' -carbonyldiimidazole, the reaction end point is tracked, 25mL of dichloromethane and 2X 15mL of deionized water are added into an organic phase for washing (2X 15mL represents that the deionized water is washed twice, each time is 15mL), liquid separation is carried out, the organic phase is dewatered by anhydrous magnesium sulfate, and liquid A is obtained after concentration.

Adding 1.2mmol of ambroxol and 20mL of N, N-dimethylformamide into the liquid A, heating to 90 ℃, and stirring for reacting for 6 h. And cooling to room temperature after reaction, adding 50mL of deionized water and 50mL of dichloromethane into the organic phase, separating the solution, washing the organic phase with 15mL of deionized water and 15mL of saturated NaCl solution in turn, removing water from the organic phase with anhydrous magnesium sulfate, concentrating to obtain an oily liquid, and then carrying out column chromatography separation, purification, concentration and drying to obtain the cinnamyl alcohol norambrox carbonate latent aroma.

Example 2

1mmol of cinnamyl alcohol and 2mmol of 1, 1' -carbonyldiimidazole are dissolved in 20mL of dry tetrahydrofuran and heated to 25 ℃ for 4h with stirring. TLC monitoring cinnamyl alcohol and reaction products of cinnamyl alcohol and 1, 1' -carbonyldiimidazole, tracking the reaction end point, adding 25mL of dichloromethane and 2X 15mL of deionized water into an organic phase, washing with water, separating liquid, removing water from the organic phase by using anhydrous magnesium sulfate, and concentrating to obtain liquid A.

Adding 1.5mmol of ambroxol and 20mL of N, N-dimethylformamide into the liquid A, heating to 60 ℃, and stirring for reacting for 6 h. And cooling to room temperature after reaction, adding 50mL of deionized water and 50mL of dichloromethane into the organic phase, separating the solution, washing the organic phase with 15mL of deionized water and 15mL of saturated NaCl solution in turn, removing water from the organic phase with anhydrous magnesium sulfate, concentrating to obtain an oily liquid, and then carrying out column chromatography separation, purification, concentration and drying to obtain the cinnamyl alcohol norambrox carbonate latent aroma.

(I) structural characterization of the target product

By infrared spectroscopy, nuclear magnetic resonance (¹H NMR and¹³c NMR and High Resolution Mass Spectrometry (HRMS) are respectively used for carrying out structural characterization on the target product cinnamyl alcohol ambergris carbonate latent aroma obtained in the example 1, and the specific data are as follows (shown in attached figures 1-4):

cinnamyl alcohol norambrox carbonate: a colorless transparent liquid.¹H NMR(300MHz,CDCl3)δ7.34(dt,J＝12.7,6.1Hz,5H),6.68(d,J＝15.9Hz,1H),6.29(dt,J＝15.9,6.4Hz,1H),4.78(dd,J＝6.4,0.8Hz,2H),4.22(t,J＝7.6Hz,2H),1.89(dt,J＝12.0,2.9Hz,1H),1.64(t,J＝11.9Hz,3H),1.40(ddd,J＝23.1,14.0,8.0Hz,5H),1.25(dd,J＝8.8,4.8Hz,2H),1.16(s,3H),1.12(t,J＝4.6Hz,2H),0.98–0.82(m,5H),0.79(s,6H)；¹³CNMR(75MHz,CDCl₃)δ155.11,136.07,134.62,128.58,128.13,126.66,122.58,73.56,69.91,68.17,57.54,55.98,44.48,41.80,39.53,38.70,33.35,33.23,24.53,23.86,21.44,20.45,18.37,15.29；IR,

ν/cm^-1:2935.09,2867.55,1742.65,1449.40,1389.14,1259.31,967.80,938.98；

HRMS:C₂₆H₃₈NaO₄The calculated value was 437.266230, found 437.266061.

(II) perfuming application of target latent aroma in tobacco

Weighing a certain amount of cinnamyl alcohol norambroxol carbonate latent aroma, dissolving with 95% ethanol, adding onto certain flue-cured tobacco type tobacco shreds according to the proportion of 0.001%, 0.005%, 0.01%, 0.05% and 0.2%, and rolling into experimental cigarettes. And (5) adding ethanol with the same proportion to the same cut tobacco, and rolling into blank cigarettes. The blank cigarette in the experiment has the defects of irritation, heavy miscellaneous gas and the like, and the comparison and the smoking evaluation show that the smoking evaluation result is shown in the following table compared with the control sample.

TABLE 1 perfuming panel test results of cinnamyl alcohol norambrox carbonate

The research on the thermal cracking product of the latent aroma shows that: the main thermal cracking products analyzed by the thermal cracking gas chromatography mass spectrogram of the latent aroma at 300 ℃ are cinnamyl alcohol and ambrox. Comparing the smoking results, the cigarette added with the latent aroma has the effects of increasing the ambergris aroma, improving the smoking taste, improving the mouthfeel, reducing the stimulation, covering the miscellaneous gas, and smoothing the smoke.

Although the invention has been described herein with reference to illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.