A compound for reducing focus, reducing irritation and releasing fragrance, a preparation method, applications and application methods

Abstract

The application discloses a compound for reducing tar and irritation and hiding aroma, a preparation method, application and application method, and has the general formula as shown in the specification.The technical scheme of the application synthesizes 7-isobutyryloxy-2-phenyl chromone by using 7-hydroxyflavone as raw material through an esterification reaction, the compound for hiding aroma is stable in property, can release 7-hydroxyflavone and corresponding organic acid during pyrolysis at high temperature, can reduce tar content of cigarettes when added into the cigarettes, can reduce irritation of smoke, can improve comfort of aftertaste, can enrich aroma of the cigarettes, and has potential application value.

Description

Technical Field

[0001] This invention relates to the field of tobacco flavoring synthesis technology, and more specifically, to a tar-reducing and pungent aroma-reducing compound, its preparation method, its application, and its application method. Background Technology

[0002] Currently, most flavorings and fragrances used in cigarette production suffer from volatility and instability, affecting the quality stability of cigarette products. However, latent aroma compounds are a class of compounds with low volatility, relatively stable chemical properties, and no aroma of their own or little effect on aroma perception. When added to cigarettes, they undergo decomposition during combustion, releasing specific aroma components and achieving the goal of stabilizing cigarette product quality. Therefore, the synthesis and application of latent aroma compounds have gradually become a research hotspot in recent years.

[0003] 7-Hydroxyflavone (7HF) is a flavonoid compound extracted from natural plants. It possesses various physiological and pharmacological activities, including anti-inflammatory and antioxidant effects, and can protect kidney cells from nicotine-induced cell damage. Its use as an additive in tobacco products is significant for reducing tar content. Derivatization of 7-hydroxyflavone to obtain novel aroma compounds, when applied to cigarettes, can simultaneously reduce tar and harshness while enhancing aroma and quality, representing an effective approach to upgrading the tar and harshness reduction technology of Chinese-style cigarettes.

[0004] Therefore, there is an urgent need for a compound that reduces tar and irritation, its preparation method, its application, and its application method. Summary of the Invention

[0005] The purpose of this invention is to provide a tar-reducing and irritation-reducing aroma compound, its preparation method, its application, and its application method, in order to solve the problems in the prior art and reduce the tar content and irritation of flue gas.

[0006] This invention provides a compound that reduces tar and irritation, and has the following general formula:

[0007] .

[0008] This invention also provides a method for preparing the above-mentioned tar-reducing and irritation-reducing latent aroma compound, comprising the following steps:

[0009] In a reaction vessel, 7-hydroxyflavonoids and organic solvents were added. Under nitrogen protection in an ice-water bath, the mixture was thoroughly mixed, and then an organic base and an acylation reagent were added sequentially. The mixture was then raised to room temperature for reaction. After the reaction was completed, the organic mixture was washed several times with water and sodium bicarbonate solution, dried, and the solvent was removed by vacuum distillation. The crude product was separated by column chromatography to obtain 7-isobutyryloxy-2-phenylchromone.

[0010] In the preparation method of the tar-reducing and irritation-reducing aroma compound as described above, preferably, the reaction time at room temperature is 2 h to 5 h, the concentration of sodium bicarbonate solution is 5% and the washing is performed three times during the washing process of the organic mixture, and the drying process is carried out by drying with anhydrous sodium sulfate.

[0011] In the preparation method of the tar-reducing and irritation-reducing aroma compound as described above, preferably, the organic solvent is one of chloroform, dichloromethane, ethyl acetate, and acetone.

[0012] In the preparation method of the tar-reducing and irritation-reducing aroma compound as described above, preferably, the organic base is pyridine or triethylamine.

[0013] In the preparation method of the tar-reducing and irritation-reducing aroma compound as described above, preferably, the molar ratio of 7-hydroxyflavone to organic base is 1:(1~1.5).

[0014] In the preparation method of the tar-reducing and irritation-reducing latent aroma compound as described above, preferably, the acylation reagent is the corresponding isobutyric anhydride or isobutyryl chloride; the molar ratio of 7-hydroxyflavone to the acylation reagent is 1:(1~1.5).

[0015] The present invention also provides an application of the above-mentioned tar-reducing and irritation-reducing latent aroma compound, wherein the tar-reducing and irritation-reducing latent aroma compound is used as a flavoring in cigarette products.

[0016] The present invention also provides a method for applying the above-mentioned tar-reducing, irritation-reducing, and aroma-reducing compounds, comprising: spraying a 7-isobutyryloxy-2-phenylchromone solution onto tobacco shreds.

[0017] The method for applying the tar-reducing, pungent, and subtle aroma compounds as described above, preferably, involves spraying the 7-isobutyryloxy-2-phenylchromone solution onto the tobacco shreds, specifically including:

[0018] Dissolve 7-isobutyryloxy-2-phenylchromone in 95% ethanol solution, dilute to a concentration of 1% by mass, and spray it evenly onto tobacco shreds. The amount of 7-isobutyryloxy-2-phenylchromone added is 10 ppm to 100 ppm by mass of tobacco shreds.

[0019] This invention provides a tar-reducing and irritation-reducing latent aroma compound, its preparation method, its application, and its application method. Using 7-hydroxyflavone as a raw material, 7-isobutyryloxy-2-phenylchromone is synthesized through an esterification reaction. This latent aroma compound is stable and can release 7-hydroxyflavone and corresponding organic acids during high-temperature pyrolysis. When added to cigarettes, it can reduce the tar content of cigarettes, reduce the irritation of smoke, improve the aftertaste comfort, and enrich the aroma of cigarettes, thus having potential application value. Attached Figure Description

[0020] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described below with reference to the accompanying drawings, wherein:

[0021] Figure 1 The 1H NMR spectrum of 7-isobutyryloxy-2-phenylchromone;

[0022] Figure 2 The image shows the carbon NMR spectrum of 7-isobutyryloxy-2-phenylchromone. Detailed Implementation

[0023] Various exemplary embodiments of the present disclosure will now be described in detail with reference to the accompanying drawings. The descriptions of the exemplary embodiments are merely illustrative and are in no way intended to limit the present disclosure or its application or use. The present disclosure may be implemented in many different forms and is not limited to the embodiments described herein. These embodiments are provided so that the present disclosure will be thorough and complete, and will fully express the scope of the disclosure to those skilled in the art. It should be noted that, unless specifically stated otherwise, the relative arrangement of components and steps, the composition of materials, numerical expressions, and values ​​set forth in these embodiments should be interpreted as exemplary only and not as limiting.

[0024] The terms “first,” “second,” and similar terms used in this disclosure do not indicate any order, quantity, or importance, but are merely used to distinguish different parts. Terms such as “including” or “contains” mean that the element preceding the term encompasses the element listed after it, and do not exclude the possibility of encompassing other elements as well. Terms such as “above” and “below” are used only to indicate relative positional relationships; when the absolute position of the described object changes, this relative positional relationship may also change accordingly.

[0025] In this disclosure, when a specific component is described as being located between a first component and a second component, an intermediary component may or may not be present between the specific component and the first or second component. When a specific component is described as connecting to other components, the specific component may be directly connected to the other components without having an intermediary component, or it may not be directly connected to the other components but may have an intermediary component.

[0026] All terms used in this disclosure (including technical or scientific terms) have the same meaning as understood by one of ordinary skill in the art to which this disclosure pertains, unless otherwise specifically defined. It should also be understood that terms defined in a general dictionary, such as a dictionary, should be interpreted as having a meaning consistent with their meaning in the context of the relevant art, and not as having an idealized or highly formalized meaning, unless expressly defined herein.

[0027] Techniques, methods, and equipment known to those skilled in the art may not be discussed in detail, but where appropriate, they should be considered part of the specification.

[0028] The following are some of the reagents and instruments used in the examples.

[0029] Main reagents: 7-hydroxyflavone, isobutyric anhydride, isobutyryl chloride, sodium bicarbonate (analytical grade, Shanghai Aladdin Biochemical Technology Co., Ltd.); chloroform, dichloromethane, ethyl acetate, acetone, pyridine, triethylamine, ethanol, anhydrous sodium sulfate (analytical grade, Sinopharm Chemical Reagent Co., Ltd.); petroleum ether, ethyl acetate (analytical grade, Shanghai Darui Fine Chemicals Co., Ltd.).

[0030] Main experimental instruments: BSA22AS single-pan electronic balance (Beijing Sartorius Instruments Co., Ltd.); SHZ-D(Ⅲ) circulating water vacuum pump (Yuhua Instruments Co., Ltd., Gongyi City, Henan Province); DHG-9030A electric thermostatic drying oven (Shanghai Jinghong Experimental Equipment Co., Ltd.); Bruker Avance III 400 MHz nuclear magnetic resonance spectrometer (Bruker Corporation, USA).

[0031] Example 1

[0032] This invention provides a compound that reduces tar and irritation, and has the following general formula:

[0033] .

[0034] Example 2

[0035] This invention also provides a method for preparing the above-mentioned tar-reducing and irritation-reducing latent aroma compound, comprising the following steps:

[0036] In a reaction vessel, 7-hydroxyflavonoids and organic solvents were added. Under nitrogen protection in an ice-water bath, the mixture was thoroughly mixed, and then an organic base and an acylation reagent were added sequentially. The mixture was then raised to room temperature for reaction. After the reaction was completed, the organic mixture was washed several times with water and sodium bicarbonate solution, dried, and the solvent was removed by vacuum distillation. The crude product was separated by column chromatography to obtain 7-isobutyryloxy-2-phenylchromone.

[0037] The chemical reaction is as follows:

[0038] .

[0039] The reaction time at room temperature is 2 h to 5 h. During the washing process of the organic mixture, the concentration of sodium bicarbonate solution is 5%, and the washing is performed three times. During the drying process, anhydrous sodium sulfate is used for drying.

[0040] Furthermore, the organic solvent is one of chloroform, dichloromethane, ethyl acetate, and acetone.

[0041] Furthermore, the organic base is pyridine or triethylamine.

[0042] Furthermore, the molar ratio of 7-hydroxyflavone to organic base is 1:(1~1.5).

[0043] Furthermore, the acylation reagent is the corresponding isobutyric anhydride or isobutyryl chloride; the molar ratio of 7-hydroxyflavone to the acylation reagent is 1:(1~1.5).

[0044] Example 3

[0045] In a 50 mL round-bottom flask, 2.38 g of 7-hydroxyflavone (10 mmol) and 20 mL of chloroform were added. The mixture was thoroughly mixed in an ice-water bath under nitrogen protection. Then, 1.52 g of triethylamine (15 mmol) and 1.81 g of isobutyryl chloride (15 mmol) were added sequentially, and the mixture was allowed to react at room temperature for 4 h. After the reaction was complete, the reaction solution was washed three times successively with water and saturated 5% sodium bicarbonate solution. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by vacuum evaporation. The crude product was separated by column chromatography, eluting with petroleum ether (V): ethyl acetate (V) = 4:1, to give 2.94 g of a pale yellow solid, 7-isobutyryloxy-2-phenylchromone, in 91.4% yield.

[0046] Example 4

[0047] In a 50 mL round-bottom flask, 2.38 g of 7-hydroxyflavone (10 mmol) and 20 mL of chloroform were added. The mixture was thoroughly mixed in an ice-water bath under nitrogen protection. Then, 1.21 g of triethylamine (12 mmol) and 1.28 g of isobutyryl chloride (12 mmol) were added sequentially, and the mixture was allowed to react at room temperature for 5 h. After the reaction was complete, the reaction solution was washed three times successively with water and saturated 5% sodium bicarbonate solution. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by vacuum evaporation. The crude product was separated by column chromatography, eluting with petroleum ether (V): ethyl acetate (V) = 4:1, to give 2.78 g of a pale yellow solid, 7-isobutyryloxy-2-phenylchromone, in 90.2% yield.

[0048] Example 5

[0049] In a 50 mL round-bottom flask, 2.38 g of 7-hydroxyflavone (10 mmol) and 20 mL of chloroform were added. The mixture was thoroughly mixed in an ice-water bath under nitrogen protection. Then, 1.18 g of pyridine (15 mmol) and 2.79 g of isobutyric anhydride (15 mmol) were added sequentially, and the mixture was allowed to react at room temperature for 3 h. After the reaction was complete, the reaction solution was washed three times successively with water and saturated 5% sodium bicarbonate solution. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by vacuum evaporation. The crude product was separated by column chromatography, eluting with petroleum ether (V): ethyl acetate (V) = 4:1, to give 2.63 g of a pale yellow solid, 7-isobutyryloxy-2-phenylchromone, in 85.3% yield.

[0050] Example 6

[0051] In a 50 mL round-bottom flask, 2.38 g of 7-hydroxyflavone (10 mmol) and 20 mL of chloroform were added. The mixture was thoroughly mixed in an ice-water bath under nitrogen protection. Then, 1.18 g of pyridine (15 mmol) and 2.79 g of isobutyric anhydride (15 mmol) were added sequentially, and the mixture was allowed to react at room temperature for 5 h. After the reaction was complete, the reaction solution was washed three times successively with water and saturated 5% sodium bicarbonate solution. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by vacuum evaporation. The crude product was separated by column chromatography, eluting with petroleum ether (V): ethyl acetate (V) = 4:1, to give 2.84 g of a pale yellow solid, 7-isobutyryloxy-2-phenylchromone, in 92.1% yield.

[0052] The structure of the target compound 7-isobutyryloxy-2-phenylchromone was detected using a Bruker Avance III 300 MHz nuclear magnetic resonance spectrometer (Bruker Corporation, USA). 1 H NMR and 13 C NMR respectively as follows Figure 1 and Figure 2 As shown.

[0053] The structural characterization data of the 7-isobutyryloxy-2-phenylchromone compound are: mp 204℃~206℃. 1 HNMR (400 MHz, CDCl3) δ: 8.769 (d, J = 8.8 Hz, 1H), 7.734 (d, J = 8.0 Hz, 1H), 7.398-7.561 (m, 4H), 6.772 (s, 1H), 6.339 (s, 2H), 3.184-3.384 (m, 1H),0.996-1.036 (m, 6H). 13C NMR (100 MHz, CDCl3) δ: 140.36, 138.99, 134.41,133.83, 130.45, 129.33, 128.97, 128.59, 127.95, 126.96, 125.32, 124.36,124.20, 117.22, 116.61, 50.16, 39.30, 36.41.

[0054] Example 7

[0055] The present invention also provides an application of the above-mentioned tar-reducing and irritation-reducing latent aroma compound, wherein the tar-reducing and irritation-reducing latent aroma compound is used as a flavoring in cigarette products.

[0056] Example 8

[0057] The present invention also provides a method for applying the above-mentioned tar-reducing, irritation-reducing, and aroma-reducing compounds, comprising: spraying a 7-isobutyryloxy-2-phenylchromone solution onto tobacco shreds.

[0058] Specifically, spraying the 7-isobutyryloxy-2-phenylchromone solution onto the tobacco shreds includes:

[0059] Dissolve 7-isobutyryloxy-2-phenylchromone in 95% ethanol solution, dilute to a concentration of 1% by mass, and spray it evenly onto tobacco shreds. The amount of 7-isobutyryloxy-2-phenylchromone added is 10 ppm to 100 ppm by mass of tobacco shreds.

[0060] Next, the application of the 7-isobutyryloxy-2-phenylchromone latent aroma compound in cigarettes was evaluated. Specifically, in some embodiments of the present invention, a certain amount of 7-isobutyryloxy-2-phenylchromone was weighed and diluted with ethanol to prepare a 1% solution for later use. 100 g of flavored and processed cigarette tobacco was weighed and evenly spread on a clean tray. The 7-isobutyryloxy-2-phenylchromone solution was evenly sprayed onto the tobacco to obtain flavored cigarette tobacco with a 7-isobutyryloxy-2-phenylchromone to tobacco specific gravity of 10 ppm, 50 ppm, and 100 ppm, respectively. The tobacco was sealed and placed for 4 h, then dried in a 100°C oven, humidified with distilled water to the standard moisture content (12%), and rolled into standard cigarettes, labeled 1#, 2#, and 3#, respectively. After balancing the moisture content (humidity 60%±2%, temperature 25°C±1°C) for 48 h, the cigarettes were evaluated. The control sample consisted of normally flavored and processed cigarettes, which were equilibrated for 48 hours under the same temperature and humidity conditions. Then, the sensory quality of the cigarettes before and after the application of 7-isobutyryloxy-2-phenylchromone was compared and evaluated using the method of national standard GB 5606.4—2005. The evaluation results are listed in Table 1.

[0061] Table 1 Sensory quality of cigarettes before and after application

[0062]

[0063] As can be seen from the evaluation results in Table 1, the application of 7-isobutyryloxy-2-phenylchromone improved the aroma, reduced off-flavors, decreased irritation, and improved aftertaste of cigarettes. However, the cigarette's overall balance deteriorated when the addition amount was 100 ppm. Among these, the cigarette achieved the best results in all indicators and the highest sensory evaluation score when the addition amount was 50 ppm. The sensory evaluation score increased from 90.00 to 91.08, the aroma score increased from 29.00 to 29.27, the off-flavor score increased from 11.00 to 11.17, the irritation score increased from 18.00 to 18.47, and the aftertaste score increased from 22.00 to 22.17. Other indicators remained basically unchanged.

[0064] Results of Cigarette Smoke Hazard Index Determination: A certain amount of 7-isobutyryloxy-2-phenylchromone was weighed and diluted with ethanol to prepare a 1% solution for later use. 100 g of flavored and processed cigarette tobacco was weighed and evenly spread on a clean tray. The 7-isobutyryloxy-2-phenylchromone solution was evenly sprayed onto the tobacco to obtain flavored cigarette tobacco with a 7-isobutyryloxy-2-phenylchromone to tobacco specific gravity of 50 ppm. The tobacco was sealed and placed for 4 h, then dried in a 100℃ oven. It was then humidified with distilled water to the standard moisture content (12%), rolled into standard cigarettes, and marked as #4. After equilibration (humidity 60%±2%, temperature 25℃±1℃) for 48 h, the cigarettes were evaluated. The control sample was a normal flavored and processed cigarette, equilibrated for 48 h under the same temperature and humidity conditions. The release amounts of seven harmful components and tar in the mainstream cigarette smoke were determined using national or industry standard methods, and the smoke hazard index (H) was calculated using Formula 1.

[0065] (1)

[0066] Where: H is the flue gas hazard assessment index; X CO X represents the measured CO emission level (mg / cigarette) in mainstream cigarette smoke. HCN X represents the measured HCN release (μg / cigarette) in mainstream cigarette smoke. NNK X represents the measured NNK emission level in mainstream cigarette smoke (ng / cigarette); NH3 X represents the measured NH3 emission level (μg / cigarette) in mainstream cigarette smoke. B[a]P X represents the measured value of B[a]P release in mainstream cigarette smoke (ng / cigarette); 苯酚 X represents the measured value of phenol release in mainstream cigarette smoke (μg / cigarette); 巴豆醛 The measured value (μg / cigarette) of crotonaldehyde release in mainstream cigarette smoke is given.

[0067] Table 2 shows the results of tar and seven harmful components release from the mainstream smoke of reference cigarettes and cigarettes with added 7-isobutyryloxy-2-phenylchromone.

[0068] Table 2. Release levels of tar and seven harmful components in mainstream cigarette smoke

[0069]

[0070] As shown in Table 2, compared with the blank reference cigarette, the release of tar and seven harmful components in the mainstream smoke of cigarettes with added 7-isobutyryloxy-2-phenylchromone was significantly reduced. This indicates that 7-isobutyryloxy-2-phenylchromone can effectively reduce tar and seven harmful components in the mainstream smoke of cigarettes, and is a highly efficient scavenger for reducing harm from cigarettes. Based on the release of tar and seven harmful components in the mainstream smoke of cigarettes, the cigarette hazard index (H) can be calculated using Formula 1, and the results are shown in Table 2. As shown in Table 2, the hazard index of the blank reference cigarette smoke was 8.76, while the hazard index of the cigarette smoke with added 7-isobutyryloxy-2-phenylchromone was 7.09. Compared with the blank reference cigarette, the hazard index of the cigarette smoke decreased by 19.06%, indicating that 7-isobutyryloxy-2-phenylchromone is a highly efficient free radical scavenger that can be used for reducing harm from cigarettes.

[0071] The tar-reducing and irritation-reducing latent aroma compound, its preparation method, application, and application method provided in this invention are synthesized from 7-hydroxyflavone via esterification. This latent aroma compound is stable and can release 7-hydroxyflavone and corresponding organic acids during high-temperature pyrolysis. When added to cigarettes, it can reduce the tar content of cigarettes, reduce the irritation of smoke, improve the aftertaste comfort, and enrich the aroma of cigarettes, thus having potential application value.

[0072] The embodiments of this disclosure have now been described in detail. To avoid obscuring the concept of this disclosure, some details known in the art have not been described. Those skilled in the art can fully understand how to implement the technical solutions disclosed herein based on the above description.

[0073] While specific embodiments of this disclosure have been described in detail by way of examples, those skilled in the art should understand that the examples are for illustrative purposes only and not intended to limit the scope of this disclosure. Those skilled in the art should understand that modifications can be made to the above embodiments or equivalent substitutions can be made to some technical features without departing from the scope and spirit of this disclosure. The scope of this disclosure is defined by the appended claims.

Claims

1. A reduced-impact, reduced-odor, reduced-strength, reduced-lingering compound, characterized in that, The compound has the following general formula: 。 2. A method of preparing the reduced-drying, reduced-piercing, and base-notes- enhancing compound of claim 1, characterized in that, The method comprises the following steps: In a reaction container, 7-hydroxyflavone and an organic solvent are added, and after being fully mixed in an ice water bath under nitrogen protection, an organic base and an acylating agent are sequentially added, and the reaction is carried out at room temperature; after the reaction is completed, the organic mixed liquid is washed with water and sodium bicarbonate solution multiple times, dried, and the solvent is removed under reduced pressure; the crude product is separated by column chromatography to obtain 7-isobutyryloxy-2-phenyl chromone.

3. The method for preparing the tar-reducing and pungent aroma compound according to claim 2, characterized in that, The reaction time at room temperature is 2 h-5 h, the concentration of the sodium bicarbonate solution is 5% during the washing of the organic mixed liquid, the washing is performed three times, and the drying is performed by using anhydrous sodium sulfate.

4. The method for preparing the tar-reducing and pungent aroma compound according to claim 2, characterized in that, The organic solvent is one of chloroform, dichloromethane, ethyl acetate and acetone.

5. The method for preparing the tar-reducing and pungent aroma compound according to claim 2, characterized in that, The organic base is pyridine or triethylamine.

6. The method for preparing the tar-reducing and pungent aroma compound according to claim 2, characterized in that, The molar ratio of 7-hydroxyflavone to the organic base is 1:(1-1.5).

7. The method for preparing the tar-reducing and pungent aroma compound according to claim 2, characterized in that, The acylating agent is corresponding isobutyric anhydride or isobutyryl chloride; the molar ratio of 7-hydroxyflavone to the acylating agent is 1:(1-1.5).

8. Use of a reduced-drying, reduced-piercing, and base-notes- enhancing compound according to claim 1, characterized in that, The compound is applied as a flavoring agent in a cigarette product.

9. The method of using a reduced-drying, reduced-piercing, and increased- aroma compound of claim 1, wherein, The method comprises the following steps: 7-isobutyryloxy-2-phenyl chromone solution is sprayed on tobacco.

10. The method of applying the tar-reducing and irritation-reducing aroma compound according to claim 9, characterized in that, The spraying of the 7-isobutyryloxy-2-phenyl chromone solution on the tobacco is specifically as follows: 7-isobutyryloxy-2-phenyl chromone is dissolved in a 95% ethanol solution, diluted to a solution with a mass percentage of 1%, and uniformly sprayed on the tobacco; the addition amount of the 7-isobutyryloxy-2-phenyl chromone is 10 ppm-100 ppm of the mass of the tobacco.

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