Tar-reducing, stabbing-reducing and aroma-suppressing compound as well as preparation method, application and application method thereof

Abstract

The invention discloses a tar-reducing, stabbing-reducing and aroma-suppressing compound as well as a preparation method, application and an application method thereof. The tar-reducing, stabbing-reducing and aroma-suppressing compound has the following general formula: # imgabs0 #. According to the technical scheme, 7-hydroxyflavone serves as a raw material, 7-isobutyryloxy-2-phenyl chromone is synthesized through esterification reaction, the precursor-aroma compound is stable in property, can release 7-hydroxyflavone and corresponding organic acid during high-temperature pyrolysis, and can reduce the tar content of cigarettes and reduce smoke irritation when being added into the cigarettes, so that the cigarette quality is improved, and the cigarette quality is improved. Meanwhile, aftertaste comfort is improved, cigarette fragrance is enriched, and potential application value is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of tobacco flavor synthesis, and more specifically to a tar-reducing and irritation-reducing latent aroma compound, a preparation method, an application and an application method. Background Art

[0002] At present, most of the flavors and fragrances used in cigarette production and processing are volatile and unstable, which affects the quality stability of cigarette products. Latent aroma compounds are a type of compound with weak volatility, relatively stable chemical properties, and no aroma or little effect on aroma. After being added to cigarettes, they will be cracked during the smoking process of cigarettes, releasing specific aroma components, achieving the purpose of stabilizing the quality of cigarette products. 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 has multiple physiological and pharmacological activities such as anti-inflammatory and antioxidant activities, and can also protect renal cells from nicotine-induced cell damage. Applying it as an additive to tobacco products is of great significance for reducing tar in tobacco products. Derivatization of 7-hydroxyflavone to obtain new latent aroma compounds can be used in cigarettes to simultaneously reduce tar and prickly odor, increase flavor and improve quality. It is an effective way to upgrade the technology of reducing tar and prickly odor in Chinese cigarettes.

[0004] Therefore, there is an urgent need for a tar-reducing, thorn-reducing and latent aroma compound, a preparation method, an application and an application method. Summary of the invention

[0005] The purpose of the present invention is to provide a tar-reducing, irritating and latent aroma compound, a preparation method, an application and an application method to solve the above-mentioned problems in the prior art, and can reduce the tar in flue gas and reduce irritation.

[0006] The present invention provides a tar-reducing, thorn-reducing and latent aroma compound having the following general formula: .

[0007] The present invention also provides a method for preparing the above-mentioned tar-reducing, thorn-reducing and aroma-potent compound, comprising the following steps:

[0008] In a reaction container, 7-hydroxyflavone and an organic solvent are added, and in an ice-water bath under nitrogen protection, an organic base and an acylating agent are added in sequence after being fully mixed, and the temperature is raised to room temperature for reaction; after the reaction is completed, the organic mixed solution is washed with water and a sodium bicarbonate solution in sequence for multiple times, dried, and the solvent is evaporated under reduced pressure. The crude product is separated by column chromatography to obtain 7-isobutyryloxy-2-phenylchromone.

[0009] The method for preparing the tar-reducing, thorn-reducing and aroma-reducing compound as described above, wherein preferably, the reaction time at room temperature is 2 h to 5 h, during the washing process of the organic mixed solution, the concentration of the sodium bicarbonate solution is 5%, the number of washing times is three times, and during the drying process, it is dried over anhydrous sodium sulfate.

[0010] In the method for preparing the tar-reducing, thorn-reducing and aroma-potent compound as described above, preferably, the organic solvent is one of chloroform, dichloromethane, ethyl acetate and acetone.

[0011] In the method for preparing the tar-reducing, thorn-reducing and aroma-potent compound as described above, preferably, the organic base is pyridine or triethylamine.

[0012] In the method for preparing the tar-reducing, thorn-reducing and aroma-potent compound as described above, preferably, the molar ratio of 7-hydroxyflavone to the organic base is 1:(1-1.5).

[0013] The method for preparing the tar-reducing, thorn-reducing and aroma-potent compound as described above, wherein preferably, the acylating agent is the corresponding isobutyric anhydride or isobutyryl chloride; and the molar ratio of 7-hydroxyflavone to the acylating agent is 1:(1-1.5).

[0014] The present invention also provides an application of the tar-reducing, sting-reducing and latent aroma compound, wherein the tar-reducing, sting-reducing and latent aroma compound is used as a flavor in a cigarette product.

[0015] The present invention also provides an application method of the tar-reducing, irritation-reducing and aroma-potent compound, comprising: spraying a 7-isobutyryloxy-2-phenylchromone solution on shredded tobacco.

[0016] The method for applying the tar-reducing, thorn-reducing and aroma-reducing latent compound as described above, wherein preferably, the step of spraying the 7-isobutyryloxy-2-phenylchromone solution on the tobacco shreds specifically comprises:

[0017] 7-isobutyryloxy-2-phenylchromone is dissolved in 95% ethanol solution, diluted to a solution with a concentration of 1% by mass, and sprayed evenly on the tobacco shreds. The addition amount of the 7-isobutyryloxy-2-phenylchromone is 10 ppm to 100 ppm of the tobacco shreds.

[0018] The invention provides a tar-reducing and irritating latent aroma compound, a preparation method, an application and an application method. 7-isobutyryloxy-2-phenylchromone is synthesized by esterification reaction using 7-hydroxyflavone as a raw material. The latent aroma compound has stable properties and can release 7-hydroxyflavone and corresponding organic acids during high-temperature pyrolysis. When added to cigarettes, the tar content of the cigarettes can be reduced, the smoke irritation can be reduced, the aftertaste comfort can be improved, and the aroma of the cigarettes can be enriched. The latent aroma compound has potential application value. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention will be further described below with reference to the accompanying drawings, in which:

[0020] Figure 1 is the H NMR spectrum of 7-isobutyryloxy-2-phenylchromone;

[0021] Figure 2 This is the carbon NMR spectrum of 7-isobutyryloxy-2-phenylchromone. DETAILED DESCRIPTION

[0022] Various exemplary embodiments of the present disclosure will now be described in detail with reference to the accompanying drawings. The description of the exemplary embodiments is merely illustrative and is in no way intended to limit the present disclosure and its application or use. The present disclosure can be implemented in many different forms and is not limited to the embodiments described herein. These embodiments are provided to make the present disclosure thorough and complete and to fully express the scope of the present disclosure to those skilled in the art. It should be noted that unless otherwise specifically stated, the relative arrangement of the components and steps, the composition of the materials, the numerical expressions and the numerical values ​​set forth in these embodiments should be interpreted as being merely exemplary and not as limiting.

[0023] The words "first", "second" and similar words used in this disclosure do not indicate any order, quantity or importance, but are only used to distinguish different parts. The words "include" or "comprises" and similar words mean that the elements before the word include the elements listed after the word, and do not exclude the possibility of including other elements. "Up", "down" and the like are only used to indicate relative positional relationships. When the absolute position of the described object changes, the relative positional relationship may also change accordingly.

[0024] In the present disclosure, when a specific component is described as being located between a first component and a second component, there may or may not be an intermediate component between the specific component and the first component or the second component. When a specific component is described as being connected to other components, the specific component may be directly connected to the other components without an intermediate component, or may not be directly connected to the other components but have an intermediate component.

[0025] All terms (including technical terms or scientific terms) used in the present disclosure have the same meanings as those understood by ordinary technicians in the field to which the present disclosure belongs, unless otherwise specifically defined. It should also be understood that terms defined in general dictionaries, such as general dictionaries, should be interpreted as having meanings consistent with their meanings in the context of the relevant technology, and should not be interpreted in an idealized or extremely formal sense, unless explicitly defined herein.

[0026] Technologies, methods, and equipment known to ordinary technicians in the relevant art may not be discussed in detail, but where appropriate, the technologies, methods, and equipment should be considered part of the specification.

[0027] The following are some of the reagents and instruments used in the examples.

[0028] 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.).

[0029] Main experimental instruments: BSA22AS single-pan electronic balance (Beijing Sartorius Instrument Co., Ltd.); SHZ-D (III) circulating water vacuum pump (Yuhua Instrument Co., Ltd., Gongyi City, Henan Province); DHG-9030A electric constant temperature blast drying oven (Shanghai Jinghong Experimental Equipment Co., Ltd.); Bruker Avance III 400 MHz nuclear magnetic resonance spectrometer (Bruker Corporation, USA).

[0030] Example 1

[0031] The present invention provides a tar-reducing, thorn-reducing and latent aroma compound having the following general formula: .

[0032] Example 2

[0033] The present invention also provides a method for preparing the above-mentioned tar-reducing, thorn-reducing and aroma-potent compound, comprising the following steps:

[0034] In a reaction container, 7-hydroxyflavone and an organic solvent are added, and in an ice-water bath under nitrogen protection, an organic base and an acylating agent are added in sequence after being fully mixed, and the temperature is raised to room temperature for reaction; after the reaction is completed, the organic mixed solution is washed with water and a sodium bicarbonate solution in sequence for multiple times, dried, and the solvent is evaporated under reduced pressure. The crude product is separated by column chromatography to obtain 7-isobutyryloxy-2-phenylchromone.

[0035] The chemical reaction is as follows:

[0036] .

[0037] The reaction time at room temperature is 2 h to 5 h. In the washing process of the organic mixed solution, the concentration of the sodium bicarbonate solution is 5%, the washing times are three times, and in the drying process, it is dried by anhydrous sodium sulfate.

[0038] Furthermore, the organic solvent is one of chloroform, dichloromethane, ethyl acetate and acetone.

[0039] Furthermore, the organic base is pyridine or triethylamine.

[0040] Furthermore, the molar ratio of 7-hydroxyflavone to the organic base is 1:(1-1.5).

[0041] Furthermore, the acylating agent is the corresponding isobutyric anhydride or isobutyryl chloride; the molar ratio of 7-hydroxyflavone to the acylating agent is 1:(1-1.5).

[0042] Example 3

[0043] In a 50 mL round-bottom flask, add 2.38 g 7-hydroxyflavone (10 mmol) and 20 mL chloroform. In an ice-water bath, under nitrogen protection, mix thoroughly, then add 1.52 g triethylamine (15 mmol) and 1.81 g isobutyryl chloride (15 mmol) in sequence, and warm to room temperature for 4 h. After the reaction, the reaction solution was washed with water and saturated 5% sodium bicarbonate solution three times in sequence. The organic phase was dried over anhydrous sodium sulfate and the solvent was evaporated under reduced pressure. The crude product was separated by column chromatography, eluted with petroleum ether (V): ethyl acetate (V) = 4:1, and 2.94 g of light yellow solid was obtained, which was 7-isobutyryloxy-2-phenylchromone, with a yield of 91.4%.

[0044] Example 4

[0045] In a 50 mL round-bottom flask, add 2.38 g 7-hydroxyflavone (10 mmol) and 20 mL chloroform. In an ice-water bath, under nitrogen protection, mix thoroughly, then add 1.21 g triethylamine (12 mmol) and 1.28 g isobutyryl chloride (12 mmol) in sequence, and warm to room temperature for 5 h. After the reaction, the reaction solution was washed with water and saturated 5% sodium bicarbonate solution three times in sequence. The organic phase was dried over anhydrous sodium sulfate and the solvent was evaporated under reduced pressure. The crude product was separated by column chromatography, eluted with petroleum ether (V): ethyl acetate (V) = 4:1, and 2.78 g of light yellow solid was obtained, which was 7-isobutyryloxy-2-phenylchromone with a yield of 90.2%.

[0046] Example 5

[0047] In a 50 mL round-bottom flask, add 2.38 g 7-hydroxyflavone (10 mmol) and 20 mL chloroform. In an ice-water bath, under nitrogen protection, mix thoroughly, then add 1.18 g pyridine (15 mmol) and 2.79 g isobutyric anhydride (15 mmol) in sequence, and warm to room temperature for 3 h. After the reaction, the reaction solution was washed with water and saturated 5% sodium bicarbonate solution three times in sequence. The organic phase was dried over anhydrous sodium sulfate and the solvent was evaporated under reduced pressure. The crude product was separated by column chromatography, eluted with petroleum ether (V): ethyl acetate (V) = 4:1, and 2.63 g of light yellow solid was obtained, which was 7-isobutyryloxy-2-phenylchromone, with a yield of 85.3%.

[0048] Example 6

[0049] In a 50 mL round-bottom flask, add 2.38 g 7-hydroxyflavone (10 mmol) and 20 mL chloroform. In an ice-water bath, under nitrogen protection, mix thoroughly, then add 1.18 g pyridine (15 mmol) and 2.79 g isobutyric anhydride (15 mmol) in sequence, and warm to room temperature for 5 h. After the reaction, the reaction solution was washed three times with water and saturated 5% sodium bicarbonate solution in sequence. The organic phase was dried over anhydrous sodium sulfate and the solvent was evaporated under reduced pressure. The crude product was separated by column chromatography, eluted with petroleum ether (V): ethyl acetate (V) = 4:1, and 2.84 g of light yellow solid was obtained, which was 7-isobutyryloxy-2-phenylchromone with a yield of 92.1%.

[0050] The present invention uses a Bruker Avance III 300 MHz nuclear magnetic resonance spectrometer (Bruker, USA) to detect the structure of the obtained target compound 7-isobutyryloxy-2-phenylchromone. 1 H NMR and 13 C NMR Figure 1 and Figure 2 shown.

[0051] The structural characterization data of 7-isobutyryloxy-2-phenylchromone compound are: mp 204℃~206℃. 1 HNMR (400 MHz, CDCl 3 ) 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). 13 C 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.

[0052] Example 7

[0053] The present invention also provides an application of the tar-reducing, sting-reducing and latent aroma compound, wherein the tar-reducing, sting-reducing and latent aroma compound is used as a flavor in a cigarette product.

[0054] Example 8

[0055] The present invention also provides an application method of the tar-reducing, irritation-reducing and aroma-potent compound, comprising: spraying a 7-isobutyryloxy-2-phenylchromone solution on shredded tobacco.

[0056] Wherein, the step of spraying the 7-isobutyryloxy-2-phenylchromone solution on the tobacco shreds specifically comprises:

[0057] 7-isobutyryloxy-2-phenylchromone is dissolved in 95% ethanol solution, diluted to a solution with a concentration of 1% by mass, and sprayed evenly on the tobacco shreds. The addition amount of the 7-isobutyryloxy-2-phenylchromone is 10 ppm to 100 ppm of the tobacco shreds.

[0058] Next, the 7-isobutyryloxy-2-phenylchromone latent aroma compound was evaluated for cigarette application. Specifically, in some embodiments of the present invention, a certain amount of 7-isobutyryloxy-2-phenylchromone was weighed and diluted with ethanol to a 1% solution for standby use. 100 g of flavored cigarette shreds were weighed and evenly spread on a clean tray, and the 7-isobutyryloxy-2-phenylchromone solution was evenly sprayed on the shredded tobacco to obtain shredded cigarettes with a ratio of 7-isobutyryloxy-2-phenylchromone to shredded tobacco of 10 ppm, 50 ppm and 100 ppm, which were sealed and placed for 4 hours, placed in a 100°C oven for drying, humidified with distilled water to a standard moisture content (12%), rolled into standard cigarettes, recorded as 1#, 2# and 3#, and balanced with moisture (humidity 60%±2%, temperature 25°C±1°C) for 48 hours before evaluation. The control sample is a normal flavored cigarette, which is balanced under the same temperature and humidity conditions for 48 hours. Then, the sensory quality of cigarettes before and after the application of 7-isobutyryloxy-2-phenylchromone is compared and evaluated using the method of national standard GB 5606.4-2005. The evaluation results are listed in Table 1.

[0059] Table 1 Sensory quality of cigarettes before and after application

[0060] From the evaluation results in Table 1, it can be seen that after the application of 7-isobutyryloxy-2-phenylchromone, the aroma of cigarettes is improved, the assorted smell is reduced, the irritation is reduced, and the aftertaste is improved. However, when the addition amount is 100 ppm, the coordination of cigarettes deteriorates. Among them, when the addition amount is 50 ppm, the cigarette indicators are the best and the sensory evaluation score is the highest. The sensory evaluation score of cigarettes is increased from 90.00 points to 91.08 points, the aroma is increased from 29.00 points to 29.27 points, the assorted smell is increased from 11.00 points to 11.17 points, the irritation is increased from 18.00 points to 18.47 points, the aftertaste is increased from 22.00 points to 22.17 points, and the other indicators are basically unchanged.

[0061] Results of the determination of the harmfulness index of cigarette smoke: Weigh a certain amount of 7-isobutyryloxy-2-phenylchromone and dilute it with ethanol to a 1% solution for later use. Weigh 100 g of flavored and flavored cigarette shreds, spread them evenly on a clean tray, and evenly spray the 7-isobutyryloxy-2-phenylchromone solution on the shredded tobacco to obtain a flavored cigarette shred with a 7-isobutyryloxy-2-phenylchromone to shredded tobacco ratio of 50 ppm. Seal and place for 4 hours, put in a 100℃ oven to dry, humidify with distilled water to the standard moisture content (12%), roll into a standard cigarette, record it as 4#, balance the moisture content (humidity 60%±2%, temperature 25℃±1℃) for 48 hours before evaluating. The control sample is a normal flavored and flavored cigarette, and the control sample is balanced under the same temperature and humidity conditions for 48 hours. The release of 7 harmful components and tar in the mainstream smoke of cigarettes is determined using national standards or industry standard methods, and the smoke harmfulness index (H) is calculated using formula 1: (1)

[0062] Where: H is the smoke hazard evaluation index; X CO is the measured value of CO release in mainstream cigarette smoke (mg / cigarette); X HCN is the measured value of HCN release in mainstream cigarette smoke (μg / cigarette); X NNK is the measured value of NNK release in mainstream cigarette smoke (ng / cigarette); X NH3 NH in mainstream cigarette smoke 3 Release amount measured value (μg / stick); X B[a]P is the measured value of B[a]P release in mainstream cigarette smoke (ng / cigarette); X 苯酚 is the measured value of phenol release in mainstream cigarette smoke (μg / cigarette); X 巴豆醛 It is the actual measured value of crotonaldehyde release in mainstream cigarette smoke (μg / cigarette).

[0063] The results of the release of tar and seven harmful components in mainstream smoke of reference cigarettes and cigarettes added with 7-isobutyryloxy-2-phenylchromone are shown in Table 2.

[0064] Table 2 Release of tar and seven harmful components in mainstream cigarette smoke

[0065] As can be seen from Table 2, compared with the blank reference cigarette, the release of tar and seven harmful components in the mainstream smoke of cigarettes with 7-isobutyryloxy-2-phenylchromone was significantly reduced, indicating 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 the harm of cigarettes. According to the release of tar and seven harmful components in the mainstream smoke of cigarettes, the cigarette hazard index (H) can be calculated by formula 1, and the results are shown in Table 2. As can be seen from Table 2, the smoke hazard index of the blank reference cigarette is 8.76, while the smoke hazard index of the cigarette with 7-isobutyryloxy-2-phenylchromone is 7.09. Compared with the blank reference cigarette, the smoke hazard index of the cigarette is reduced by 19.06%, indicating that 7-isobutyryloxy-2-phenylchromone is a highly efficient free radical scavenger that can be used for cigarette harm reduction.

[0066] The tar-reducing and irritation-reducing latent aroma compound, preparation method, application and application method provided in the embodiments of the present invention use 7-hydroxyflavone as a raw material, and synthesize 7-isobutyryloxy-2-phenylchromone through esterification reaction. The latent aroma compound is stable in nature, 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 and reduce the irritation of smoke, while improving the comfort of aftertaste and enriching the aroma of cigarettes, and has potential application value.

[0067] So far, various embodiments of the present disclosure have been described in detail. In order to avoid obscuring the concept of the present disclosure, some details known in the art are not described. Based on the above description, those skilled in the art can fully understand how to implement the technical solution disclosed here.

[0068] Although some specific embodiments of the present disclosure have been described in detail by way of examples, it should be understood by those skilled in the art that the above examples are for illustration only and are not intended to limit the scope of the present disclosure. It should be understood by those skilled in the art that the above embodiments may be modified or some technical features may be replaced by equivalents without departing from the scope and spirit of the present disclosure. The scope of the present disclosure is defined by the appended claims.

Claims

1. A compound for reducing tar and thorn and latent aroma, characterized in that: Has the following general formula: 。 2. A method for preparing the tar-reducing, thorn-reducing and aroma-potent compound according to claim 1, characterized in that: The following steps are involved: In a reaction container, 7-hydroxyflavone and an organic solvent are added, and in an ice-water bath under nitrogen protection, an organic base and an acylating agent are added in sequence after being fully mixed, and the temperature is raised to room temperature for reaction; after the reaction is completed, the organic mixed solution is washed with water and a sodium bicarbonate solution in sequence for multiple times, dried, and the solvent is evaporated under reduced pressure. The crude product is separated by column chromatography to obtain 7-isobutyryloxy-2-phenylchromone.

3. The method for preparing the tar-reducing, thorn-reducing and aroma-potent compound according to claim 2, characterized in that: The reaction time at room temperature is 2 h~5 h. In the washing process of the organic mixed solution, the concentration of the sodium bicarbonate solution is 5%, the washing times are three times, and in the drying process, it is dried over anhydrous sodium sulfate.

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

6. The method for preparing the tar-reducing, thorn-reducing and aroma-potent 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, thorn-reducing and aroma-potent 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. The use of the tar-reducing, thorn-reducing and aroma-potent compound according to claim 1, characterized in that: The tar-reducing and sting-reducing latent aroma compound is used as a flavor in cigarette products.

9. The application method of the tar-reducing, thorn-reducing and aroma-potent compound according to claim 1, characterized in that: include: The 7-isobutyryloxy-2-phenylchromone solution is sprayed on the tobacco shreds.

10. The application method of the tar-reducing, thorn-reducing and aroma-potent compound according to claim 9, characterized in that: The step of spraying the 7-isobutyryloxy-2-phenylchromone solution on the tobacco shreds specifically comprises: 7-isobutyryloxy-2-phenylchromone is dissolved in 95% ethanol solution, diluted to a solution with a concentration of 1% by mass, and sprayed evenly on the tobacco shreds. The addition amount of the 7-isobutyryloxy-2-phenylchromone is 10 ppm to 100 ppm of the tobacco shreds.

Images