Composite floral-fruit fragrance type cryptic fragrance compounds, preparation method, application and application method
The preparation of chemically stable methyl 2-amide benzoate via acylation reaction solves the problem of unstable volatility in cigarette flavorings, imparts fruity and sweet notes to cigarettes, and achieves stable flavoring addition.
Patent Information
- Application Number
- CN202411728548.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-28
- Publication Date
- 2025-11-18
- Estimated Expiration
- 2044-11-28
AI Technical Summary
Existing cigarette flavorings are volatile and unstable, affecting the stability of cigarette quality. Methyl 2-aminobenzoate is prone to discoloration and volatilization during storage. Stable flavor precursors need to be developed to enrich the tobacco aroma and increase sweetness.
Methyl 2-aminobenzoate was derivatized into methyl 2-amidobenzoate via acylation to prepare a chemically stable complex floral and fruity aroma compound. When added to cigarettes, it can release specific aroma components during high-temperature pyrolysis.
It achieves storage stability and flavoring stability of complex floral and fruity aroma compounds, imparts fruity aroma characteristics to cigarettes and increases oral sweetness.
Smart Images
Figure CN119504481B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of tobacco flavor preparation, and more particularly to a composite floral and fruity latent flavor compound, a preparation method, an application and an application method. BACKGROUND
[0002] At present, most of the flavoring agents used in cigarette production and processing have the problems of easy volatilization and instability, which affect the quality stability of cigarette products. Latent flavor compounds, a kind of compound with weak volatility, relatively stable chemical properties and little or no effect on fragrance, can release specific fragrance components after cracking after combustion when added to cigarettes, and have gradually become a research hotspot in recent years.
[0003] Methyl anthranilate (MA) is a compound with sweet floral and grape-like odor, which naturally exists in grapes, strawberries, red wine and white wine. When added to tobacco, it can enrich the tobacco aroma and improve the sweetness and smoothness. However, methyl anthranilate is prone to discoloration due to light during storage, and will volatilize with water vapor, so it is of great significance to study the derivatization of methyl anthranilate to obtain stable flavor precursors.
[0004] Therefore, there is an urgent need for a composite floral and fruity latent flavor compound, a preparation method, an application and an application method. SUMMARY
[0005] The purpose of the present application is to provide a composite floral and fruity latent flavor compound, a preparation method, an application and an application method, to solve the problems in the prior art, have good storage stability and flavoring stability, and can impart floral and fruity characteristics to cigarettes and increase the sweetness and smoothness in the mouth.
[0006] The present application provides a composite floral and fruity latent flavor compound, which has the following general formula:
[0007]
[0008] wherein R represents or .
[0009] The present application also provides a preparation method of the above-mentioned composite floral and fruity latent flavor compound, comprising the following steps:
[0010] In a reaction container, methyl 2-aminobenzoate and an organic solvent are added, and under nitrogen protection, an organic base and an acylation reagent are sequentially added, and stirred at room temperature; then, the temperature is raised, and the reaction is stirred; after the reaction is completed, hydrochloric acid solution is added to the mixture, and the aqueous phase and the organic phase are separated, and the aqueous phase is extracted twice with dichloromethane, and then the organic phases are combined and dried; after drying, the organic solvent is removed to obtain a crude product, which is then recrystallized, and filtered and dried to obtain methyl 2-amidobenzoate.
[0011] The preparation method of the complex floral and fruity latent fragrance compound as described above, wherein preferably, the stirring time at room temperature is 1 h-2 h; the stirring reaction temperature is 40℃-80℃, and the stirring reaction time is 3 h-5 h; after the reaction is completed, the concentration of the hydrochloric acid solution added to the mixture is 3 mol / L, the separation is performed by a separatory funnel during the separation of the aqueous phase and the organic phase, and the drying is performed by anhydrous magnesium sulfate after the combination of the organic phases; after drying, the organic solvent is removed by a rotary evaporation method, and recrystallization is performed by anhydrous ethanol during recrystallization.
[0012] The preparation method of the complex floral and fruity latent fragrance compound as described above, wherein preferably, the organic solvent is one of dichloromethane, trichloromethane, toluene and tetrahydrofuran.
[0013] The preparation method of the complex floral and fruity latent fragrance compound as described above, wherein preferably, the organic base is one of triethylamine and pyridine.
[0014] The preparation method of the complex floral and fruity latent fragrance compound as described above, wherein preferably, the acylation reagent is corresponding benzene acetyl chloride and cinnamoyl chloride.
[0015] The preparation method of the complex floral and fruity latent fragrance compound as described above, wherein preferably, the molar ratio of methyl 2-aminobenzoate, the organic base and the acylation reagent is 1:(1-1.5):(1-1.5).
[0016] The application further provides an application of the complex floral and fruity latent fragrance compound, and the complex floral and fruity latent fragrance compound is applied as a flavor in a cigarette product.
[0017] The application further provides an application method of the complex floral and fruity latent fragrance compound, which comprises: spraying a methyl 2-amidobenzoate solution onto tobacco shreds, or preparing a methyl 2-amidobenzoate into a sizing agent, and applying the sizing agent to cigarette paper in an offline coating mode to obtain flavored cigarette paper.
[0018] The application method of the complex floral and fruity latent fragrance compound as described above, wherein preferably, the spraying of the methyl 2-amidobenzoate solution onto the tobacco shreds specifically comprises:
[0019] Methyl 2-amidobenzoate is dissolved in 95% ethanol solution, diluted to a solution with a mass percentage of 5%, and then uniformly sprayed on the tobacco shreds, with an addition amount of 1-20 ppm of the methyl 2-amidobenzoate based on the mass of the tobacco shreds,
[0020] The methyl 2-amidobenzoate is prepared into a sizing agent, which is applied to the cigarette paper in an offline coating manner to obtain a flavored cigarette paper, and specifically comprises the following steps:
[0021] A sizing agent is prepared, and the composition of the sizing agent is 1-10% of methyl 2-amidobenzoate, 0.5-1% of a combustion improver, 60-75% of ethanol and 14-38.5% of water in percentage by weight; a cigarette paper that has undergone beating, papermaking, molding, dewatering, embossing and drying processes is surface-sized in an offline coating manner and dried for the second time at 60-80℃ to obtain a flavored cigarette paper, wherein the addition amount of the sizing agent in the cigarette paper is 5-20 mg / m 2 .
[0022] The application provides a composite flower and fruit flavor type latent fragrance compound, a preparation method, application and application method, and two acylated derivatives are prepared from methyl 2-aminobenzoate through an acylation reaction, the two compounds are stable in chemical properties, and can release methyl 2-aminobenzoate and phenylacetic acid (cinnamic acid) when pyrolyzed at high temperature, and can be applied to cigarettes as stable flavor precursors to improve smoke and impart flower and fruit flavor to cigarettes. BRIEF DESCRIPTION OF DRAWINGS
[0023] In order to make the purpose, technical scheme and advantages of the application clearer, the application will be further described below with reference to the drawings, in which:
[0024] Figure 1 It is a nuclear magnetic resonance hydrogen spectrum of methyl 2-phenylacetamidobenzoate;
[0025] Figure 2 It is a nuclear magnetic resonance carbon spectrum of methyl 2-phenylacetamidobenzoate;
[0026] Figure 3 It is a nuclear magnetic resonance hydrogen spectrum of methyl 2-(3-phenyl-2-propenamido)benzoate;
[0027] Figure 4 It is a nuclear magnetic resonance carbon spectrum of methyl 2-(3-phenyl-2-propenamido)benzoate;
[0028] Figure 5 It is a sensory evaluation result of flavored cigarette paper made of compound 1;
[0029] Figure 6The results of the sensory evaluation of the flavored cigarette paper made for compound 2. DETAILED DESCRIPTION
[0030] 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 in nature and is in no way intended to limit the disclosure, its application or uses, except as described by the appended claims. The present disclosure can be implemented in numerous different forms, as is desired for specific applications; it is therefore not
[0031] The terms "first", "second", and similar terms in the present disclosure do not denote any order, quantity, or importance, but are used to distinguish different parts. The terms "include", "comprise" and the like are intended to mean that the elements listed before the terms encompass the elements listed after the terms, and do not exclude the possibility of also encompassing other elements. "Upper", "lower" and the like are used only to indicate relative positional relationships, and when the absolute position of the described object is changed, the relative positional relationship can also be changed accordingly.
[0032] In the present disclosure, when it is described that a specific component is located between a first component and a second component, there can be an intervening component between the specific component and the first component or the second component, or there can be no intervening component. When it is described that a specific component is connected to other components, the specific component can be directly connected to the other components without an intervening component, or can not be directly connected to the other components with an intervening component.
[0033] All terms used in the present disclosure, including technical or scientific terms, have the same meanings as those understood by a person of ordinary skill in the art to which the present disclosure pertains, unless otherwise specifically defined. It should also be understood that terms such as those defined in commonly used dictionaries should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and not in an idealized or overly formal sense, unless otherwise specifically defined herein.
[0034] Techniques, methods, and equipment known to those of ordinary skill in the relevant art can not be discussed in detail, but should be considered as part of the specification where appropriate.
[0035] The following are the reagents and instruments used in the examples.
[0036] 2-Aminobenzoic acid methyl ester, phenylacetyl chloride, cinnamoyl chloride (analytical pure, Shanghai Aladdin Bio-Chem Technology Co., Ltd.); triethylamine, pyridine, anhydrous ethanol, hydrochloric acid (analytical pure, China National Pharmaceutical Group Chemical Reagent Co., Ltd.); dichloromethane, chloroform, toluene, tetrahydrofuran, anhydrous magnesium sulfate (analytical pure, Beijing Chemical Plant).
[0037] 0.1 mg analytical balance (Sartorius, Germany); DF-101S heat collecting constant temperature heating magnetic stirrer (YuHua Instrument Co., Ltd., Gongyi, Henan); SHZ-D (III) circulating water type vacuum pump (YuHua Instrument Co., Ltd., Gongyi, Henan); rotary evaporator (IKA Group, Germany); Bruker Avance AMX-600 nuclear magnetic resonance spectrometer (Bruker, USA).
[0038] Example 1
[0039] The present application provides a kind of compound flower fruit fragrance type latent fragrance compound, with the following general formula:
[0040]
[0041] Wherein, R represents Corresponding to 2-phenylacetamidobenzoic acid methyl ester (compound 1) or Corresponding to 2-(3-phenyl-2-propenamido) methyl benzoate (compound 2).
[0042] Example 2
[0043] The present application also provides a kind of preparation method of the above-mentioned compound flower fruit fragrance type latent fragrance compound, comprising the following steps:
[0044] In the reaction container, 2-amino benzoic acid methyl ester and organic solvent are added, and under nitrogen protection, organic base and acylation reagent are sequentially added, and stirred at room temperature;Subsequently, heating, stirring reaction;After reaction, hydrochloric acid solution is added to the mixture, and the aqueous phase and organic phase are separated, and the aqueous phase is extracted twice with dichloromethane, and then the organic phase is combined and dried;After drying, the organic solvent is removed to obtain the crude product, then recrystallized, and filtered, dried to obtain 2-amido benzoic acid methyl ester.
[0045] Chemical reaction is as follows:
[0046] ,
[0047] The structural formula of compound 1 is:
[0048] ,
[0049] The structural formula of compound 2 is:
[0050] .
[0051] The stirring time at room temperature was 1 h to 2 h; the stirring temperature was 40℃ to 80℃, and the stirring time was 3 h to 5 h; after the reaction, the concentration of hydrochloric acid solution added to the mixture was 3 mol / L; the aqueous phase and organic phase were separated by a separatory funnel; after the organic phase was combined, it was dried with anhydrous magnesium sulfate; after drying, the organic solvent was removed by rotary evaporation; and recrystallization was carried out with anhydrous ethanol.
[0052] Furthermore, the organic solvent is one of dichloromethane, trichloromethane, toluene, and tetrahydrofuran.
[0053] Furthermore, the organic base is one of triethylamine and pyridine.
[0054] Furthermore, the acylation reagent is the corresponding phenylacetyl chloride and cinnamoyl chloride.
[0055] Furthermore, the molar ratio of methyl 2-aminobenzoate, organic base and acylation reagent is 1:(1~1.5):(1~1.5).
[0056] Example 3
[0057] In a 100 mL round-bottom flask, 3.02 g of methyl 2-aminobenzoate (20 mmol) and 30 mL of anhydrous dichloromethane were added. Under nitrogen protection, 2.43 g of triethylamine (24 mmol) and 3.71 g of phenylacetyl chloride (24 mmol) were added sequentially. The mixture was stirred at room temperature for 2 h, then heated to 40 °C for 5 h. After the reaction was completed, 15 mL of hydrochloric acid solution (3 mol / L) was added to the mixture. The aqueous and organic phases were separated by a separatory funnel. The aqueous phase was extracted twice with dichloromethane. The organic phases were then combined and dried over anhydrous magnesium sulfate. After drying, the organic solvent was removed by rotary evaporation to obtain the crude product. The crude product was recrystallized from ethanol to obtain 3.14 g of methyl 2-phenylacetamidobenzoate (compound 1), with a yield of 58.3%.
[0058] Example 4
[0059] In a 100 mL round-bottom flask, 3.02 g of methyl 2-aminobenzoate (20 mmol) and 30 mL of anhydrous chloroform were added. Under nitrogen protection, 2.43 g of triethylamine (24 mmol) and 3.71 g of phenylacetyl chloride (24 mmol) were added sequentially. The mixture was stirred at room temperature for 2 h, then heated to 65 °C for 5 h. After the reaction was completed, 15 mL of hydrochloric acid solution (3 mol / L) was added to the mixture. The aqueous and organic phases were separated by a separatory funnel. The aqueous phase was extracted twice with dichloromethane. The organic phases were then combined and dried over anhydrous magnesium sulfate. After drying, the organic solvent was removed by rotary evaporation to obtain the crude product. The crude product was recrystallized from ethanol to obtain 4.15 g of methyl 2-phenylacetamidobenzoate (compound 1), with a yield of 77.1%.
[0060] Example 5
[0061] In a 100 mL round-bottom flask, 3.02 g of methyl 2-aminobenzoate (20 mmol) and 30 mL of anhydrous toluene were added. Under nitrogen protection, 2.43 g of triethylamine (24 mmol) and 3.71 g of phenylacetyl chloride (24 mmol) were added sequentially. The mixture was stirred at room temperature for 2 h, then heated to 80 °C for 5 h. After the reaction was completed, 15 mL of hydrochloric acid solution (3 mol / L) was added to the mixture. The aqueous and organic phases were separated by a separatory funnel. The aqueous phase was extracted twice with dichloromethane. The organic phases were then combined and dried over anhydrous magnesium sulfate. After drying, the organic solvent was removed by rotary evaporation to obtain the crude product. The crude product was recrystallized from ethanol to obtain 4.61 g of methyl 2-phenylacetamidobenzoate (compound 1), with a yield of 85.6%.
[0062] Example 6
[0063] In a 100 mL round-bottom flask, 3.02 g of methyl 2-aminobenzoate (20 mmol) and 30 mL of anhydrous toluene were added. Under nitrogen protection, 2.43 g of triethylamine (24 mmol) and 4.00 g of cinnamyl chloride (24 mmol) were added sequentially. The mixture was stirred at room temperature for 2 h, then heated to 80 °C for 5 h. After the reaction was completed, 15 mL of hydrochloric acid solution (3 mol / L) was added to the mixture. The aqueous and organic phases were separated by a separatory funnel. The aqueous phase was extracted twice with dichloromethane. The organic phases were then combined and dried over anhydrous magnesium sulfate. After drying, the organic solvent was removed by rotary evaporation to obtain the crude product. The crude product was recrystallized from ethanol to give 4.72 g of methyl 2-(3-phenyl-2-acrylamido)benzoate (compound 2), with a yield of 83.9%.
[0064] Figure 1 and Figure 2The 1H and 1C NMR spectra of methyl 2-phenylacetamiobenzoate (compound 1) are shown. The structural characterization data of compound 1 are as follows: 1H NMR (400 MHz, CDCl3) δ: 8.220 (d, J = 6.8 Hz, 1H), 8.038 (d, J = 7.2 Hz, 2H), 7.537 (d, J = 8.8 Hz, 1H), 7.437 (t, J = 8.0 Hz, 2H), 7.320 (d, J = 7.6 Hz, 1H), 7.129 (t, J = 8.0 Hz, 1H), 6.784 (t, J = 6.8 Hz, 1H), 3.804 (s, 2H), 3.792 (s, 1H), 1.253 (s, 2H). 3H). 13C NMR (100 MHz, CDCl3) δ: 171.79, 141.63, 135.93, 134.07, 128.62, 127.44, 126.93,126.6,2 124.81, 124.14, 122.78, 117.36, 111.71, 101.57, 49.40, 14.11.
[0065] Figure 3 and Figure 4 The 1H and 1C NMR spectra of methyl 2-(3-phenyl-2-acrylamido)benzoate (compound 2) are shown. The structural characterization data of compound 2 are as follows: 1H NMR (400 MHz, CDCl3) δ: 8.318 (d, J = 6.8 Hz, 1H), 7.972 (d, J = 8.0 Hz, 1H), 7.457 (d, J = 8.8 Hz, 1H), 7.166–7.230 (m, 3H), 7.008 (d, J = 8.0 Hz, 1H), 6.840–6.887 (m, 2H), 4.172 (d, J = 7.2 Hz, 1H), 3.813 (d, J = 7.2 Hz, 1H), 3.776 (s, 1H). 1.239(s, 3H). 13C NMR (100 MHz, CDCl3) δ: 171.64, 157.26, 138.96, 134.67, 128.87,125.89, 124.83, 123.40, 122.59, 118.71, 117.16, 116.66, 115.87, 112.13, 61.12, 48.81, 13.90.
[0066] Example 7
[0067] The present invention also provides an application of the above-mentioned complex floral and fruity aroma latent fragrance compound, wherein the complex floral and fruity aroma latent fragrance compound is used as a flavoring in cigarette products.
[0068] Example 8
[0069] The present invention also provides a method for applying the above-mentioned composite floral and fruity aroma compounds, comprising: spraying a methyl 2-amidobenzoate solution onto tobacco shreds, or preparing methyl 2-amidobenzoate into a sizing agent and applying it onto cigarette paper by offline coating to obtain flavored cigarette paper.
[0070] Specifically, spraying the methyl 2-amidobenzoate solution onto the tobacco shreds includes:
[0071] Methyl 2-amidobenzoate is dissolved in a 95% ethanol solution and diluted to a concentration of 5% by mass. Then, it is evenly sprayed onto tobacco shreds. The amount of methyl 2-amidobenzoate added is 1 ppm to 20 ppm by mass of tobacco shreds.
[0072] Furthermore, the step of preparing methyl 2-amidobenzoate as a sizing agent and applying it to cigarette paper via offline coating to obtain flavored cigarette paper specifically includes:
[0073] A sizing agent is prepared, comprising, by weight percentage, (1-10)% methyl 2-amidobenzoate, (0.5-1)% combustion aid, (60-75)% ethanol, and (14-38.5)% water; cigarette paper that has undergone pulping, papermaking, forming, dehydration, embossing, and drying processes is surface-sized by offline coating and then dried twice at 60-80°C to obtain flavored cigarette paper, wherein the amount of sizing agent added to the cigarette paper is (5-20) mg / m³. 2 .
[0074] Next, the cigarette application of compounds 1 and 2 was evaluated. Specifically, in some embodiments of the present invention, a certain amount of methyl 2-phenylacetamidobenzoate (compound 1) and methyl 2-(3-phenyl-2-acrylamido)benzoate (compound 2) were weighed and diluted with ethanol to prepare a 5% solution for later use. 100 g of unflavored and untreated blank cigarette tobacco was weighed and evenly spread on a clean tray. The solutions of compounds 1 and 2 were evenly sprayed onto the tobacco to prepare cigarette tobacco with specific gravities of 1 ppm, 10 ppm, and 20 ppm, respectively. The tobacco was sealed and placed for 4 h, then dried in a 50°C oven, humidified with distilled water to the standard moisture content (12%), rolled into standard cigarettes, and equilibrated for 48 h (humidity 60% ± 2%, temperature 22°C ± 1°C) before sensory evaluation. The results are shown in Table 1.
[0075] Table 1. Sensory style evaluation results of compound 1 and compound 2
[0076]
[0077] In some embodiments of the present invention, methyl 2-phenylacetamidobenzoate (compound 1) and methyl 2-(3-phenyl-2-acrylamido)benzoate (compound 2) are respectively added to cigarette paper by offline coating. The composition of the sizing agent is shown in Table 2, and the coating amount of the prepared fragrance is 10 mg / m². 2 Cigarette products are manufactured using conventional techniques in the field, and then sensory evaluation is performed. For example... Figure 5 and Figure 6 As shown, compared with the blank sample without the flavoring of this application, the cigarette sample with the added flavoring has a sweeter and smoother taste, a distinct fruity aroma, a slight floral aroma, and a reduced irritation.
[0078] Table 2 Composition of sizing agent
[0079]
[0080] The present invention provides a composite floral and fruity aroma compound, its preparation method, its application, and its application method. Using methyl 2-aminobenzoate as a raw material, two acylated derivatives were prepared through an acylation reaction. These two compounds are chemically stable and can release methyl 2-aminobenzoate and phenylacetic acid (cinnamic acid) during high-temperature pyrolysis. They can be applied as stable aroma precursors to cigarettes to improve the smoke and impart a floral and fruity aroma to the cigarettes.
[0081] 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.
[0082] 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. The application of a complex floral-fruity aroma latent fragrance compound as a flavoring in cigarette products, wherein the complex floral-fruity aroma latent fragrance compound has the following general formula: ,in, R represents or .
2. The application of the complex floral and fruity aroma compound as a flavoring agent in cigarette products according to claim 1, characterized in that, Application methods include: spraying a solution of compound floral and fruity aroma compounds onto tobacco shreds.
3. The application of the complex floral and fruity aroma compound as a flavoring agent in cigarette products according to claim 2, characterized in that, The process of spraying a solution of complex floral and fruity aroma compounds onto tobacco shreds includes: The compound of floral and fruity aroma is dissolved in a 95% ethanol solution and diluted to a concentration of 5% by mass. Then, it is evenly sprayed onto the tobacco. The amount of the compound of floral and fruity aroma added is 1 ppm to 20 ppm by mass of the tobacco.
4. The application of the complex floral and fruity aroma compound as a flavoring agent in cigarette products according to claim 1, characterized in that, Application methods include: A compound of floral and fruity aroma compounds is made into a sizing agent and applied to cigarette paper by offline coating to obtain flavored cigarette paper.
5. The application of the complex floral and fruity aroma compound according to claim 4 as a flavoring agent in cigarette products, characterized in that, The process of preparing a sizing agent from a complex floral and fruity aroma compound and applying it to cigarette paper via an offline coating method to obtain flavored cigarette paper includes: A sizing agent is prepared, comprising, by weight percentage, 1%-10% of a complex floral and fruity aroma compound, 0.5%-1% of a combustion aid, 60%-75% of ethanol, and 14%-38.5% of water. Cigarette paper, having undergone pulping, papermaking, forming, dehydration, embossing, and drying processes, is surface-sized using an offline coating method and then dried twice at 60℃-80℃ to obtain flavored cigarette paper. The amount of sizing agent added to the cigarette paper is 5 mg / m³. 2 ~20mg / m 2 .