A tobacco flavor material highlighting the sweet characteristics of a cigarette, and a preparation method and application thereof

Abstract

The application discloses a tobacco flavor material highlighting the sweet characteristics of cigarettes, and a preparation method and application thereof, and has the structural formula as follows: The preparation method of the tobacco flavor material comprises the following steps: firstly, raw materials, i.e., 1,4:3,6-dianhydro-D-glucopyranose, acid, a catalyst, an additive and an organic solvent, are added into a reaction bottle; the reaction system is uniformly stirred; and the reaction is carried out at 120-200 DEG C for 12-24 hours; after the reaction is completed, dichloromethane and saturated sodium chloride solution are added; organic phase is obtained through extraction and separation, and is dried with anhydrous sodium sulfate; the reaction solvent is evaporated; the residual product is purified through a silica gel column chromatography method; and the target product is obtained. A series of dehydrated sugar long-chain ester compounds are synthesized by taking 1,4:3,6-dianhydro-D-glucopyranose as a starting raw material. When the flavor is added into cigarettes, the tobacco aroma can be enriched, the ester sweet aroma and the burnt aroma can be endowed to the cigarettes, and the aftertaste comfort can be improved.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and in particular to a fragrance raw material capable of highlighting the sweet taste of cigarettes, a preparation method thereof, and applications thereof. Background Art

[0002] 1,4:3,6-dianhydro-D-pyranose is commonly found in cigarette smoke and sugar decomposition products. It is a pyran compound produced by sugar degradation. It has the characteristics of volatility, fat solubility and water solubility, and can increase the sweetness of cigarettes.

[0003] Ester compounds have prominent aroma characteristics such as fruity sweetness and floral fragrance, and can also improve the softness of smoke. They are widely used in cigarette flavoring.

[0004] Therefore, chemical synthesis can be used to design and synthesize compounds that have the advantages of both, and add them to cigarettes as tobacco flavorings. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a fragrance raw material that highlights the sweetness characteristics of cigarettes, as well as its preparation method and application. A series of dehydrated sugar long-chain ester compounds are synthesized, which have both sweet and caramel aromas.

[0006] The technical problem to be solved by the present invention is achieved through the following technical solutions:

[0007] A fragrance raw material that highlights the sweet taste of cigarettes, the structural formula of the fragrance raw material is as follows:

[0008]

[0009] A method for preparing a fragrant raw material that highlights the sweet taste of cigarettes, comprising the following steps:

[0010]

[0011] (1) In a reaction flask, first add the raw material 1,4:3,6-dianhydro-D-pyranose, acid, catalyst, additives and organic solvent, stir the reaction system evenly, and react at 120-200°C for 12-24 hours;

[0012] (2) After the reaction, dichloromethane and saturated sodium chloride solution were added, and the organic phase was extracted and separated, and dried over anhydrous sodium sulfate. The reaction solvent was evaporated, and the residue was purified by silica gel column chromatography to obtain the target product.

[0013] Preferably, in the above technical solution, in step (1), the catalyst is scandium trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate or lanthanum trifluoromethanesulfonate, and the additive is one or more of benzenesulfonic acid, p-toluenesulfonic acid or p-methoxybenzenesulfonic acid.

[0014] Preferably, in the above technical solution, in step (1), the acid is a long-chain saturated fatty acid, preferably hexadecanoic acid, heptadecanoic acid, octadecanoic acid or nonadecanoic acid; and the organic solvent is toluene.

[0015] Preferably, in the above technical solution, in step (1), the molar ratio of the raw material 1,4:3,6-dianhydro-D-pyranose, acid, catalyst and additive is 1:(1.0-3.0):(0.1-0.5):(0.5-3.0).

[0016] Preferably, in the above technical solution, in step (2), the volume ratio of dichloromethane and saturated sodium chloride solution to the solution of step (1) is 1:1-1:2, the volume ratio of dichloromethane and saturated sodium chloride is 1:1, and the extraction time is 1-5 min.

[0017] Preferably, in the above technical solution, in step (2), the silica gel column chromatography uses petroleum ether and ethyl acetate as eluents in a volume ratio of 3:1-1:1, and gradient elution.

[0018] The invention discloses an application of a flavor raw material for highlighting the sweet taste of cigarettes in cigarettes.

[0019] Preferably, in the above technical solution, the aromatic raw material that highlights the sweet taste characteristics of cigarettes is applied to cigarettes as a flavoring, and the added amount is 1 to 50 ppm based on the mass of cigarette tobacco.

[0020] A cigarette comprising a flavoring material that accentuates the sweet flavor characteristics of the cigarette.

[0021] The above technical solution of the present invention has the following beneficial effects:

[0022] This application synthesizes a series of anhydrosugar long-chain ester compounds using 1,4:3,6-dianhydro-D-pyranose as the starting material. Adding this flavoring to cigarettes can enrich the tobacco flavor, impart sweet and burnt ester aromas to the cigarettes, and improve the aftertaste comfort. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.

[0024] Figure 1 The compound obtained in Example 1 1 H NMR spectrum;

[0025] Figure 2 The compound obtained in Example 1 13 C NMR spectrum. DETAILED DESCRIPTION

[0026] Various exemplary embodiments of the present invention will now be described in detail with reference to the accompanying drawings. It should be noted that unless otherwise specifically stated, the relative arrangement of components and steps, numerical expressions and numerical values ​​set forth in these embodiments do not limit the scope of the present invention.

[0027] Unless otherwise specified, the reagents used in this application are all commercially available or obtained through commercial channels, or can be prepared by referring to existing chemical methods.

[0028] Example 1

[0029] A method for preparing a fragrant raw material that highlights the sweet taste of cigarettes:

[0030] (1) In a 100 mL round-bottom flask, 1.44 g (10 mmol) of 1,4:3,6-dianhydro-D-pyranose glucose, 2.56 g (10 mmol) of hexadecanoic acid, 0.49 g (1 mmol) of scandium trifluoromethanesulfonate, 1.72 g (10 mmol) of p-toluenesulfonic acid, and 20 mL of toluene were added. The reaction system was stirred evenly and reacted at 120°C for 12 h.

[0031] (2) After the reaction, dichloromethane and saturated sodium chloride solution (volume ratio 1:1) were added, and the organic phase was separated by extraction for 1-5 minutes and dried over anhydrous sodium sulfate. The reaction solvent was evaporated and the residue was purified by silica gel column chromatography (using petroleum ether and ethyl acetate as eluents, volume ratio 3:1-1:1, gradient elution) to obtain 2.49 g of 1,4:3,6-dianhydro-D-pyranose hexadecanoate, with a yield of 65.3%.

[0032] Characterization: 1 H NMR (400MHz, CDCl3) δ5.53(s,1H),5.21–5.15(m,1H),4.59(s,1H),4.25(dd,J=5.1,2.3Hz,2H),4.08(d,J=10.8Hz ,1H),3.96(dd,J=10.8,2.4Hz,1H),2.32(t,J=7.6Hz,2H),1.66~1.57(m,2H),1.25(s,25H),0.88(t,J=6.8Hz,3H). 13 C NMR (400MHz, CDCl3) δ172.72,99.09,80.51,79.55,79.51,75.91,71.79,34.01,31.93 ,29.69,29.67,29.66,29.64,29.59,29.43,29.37,29.21,29.07,24.80,22.70,14.14.

[0033] The structural formula of the target compound is shown in Formula I below:

[0034]

[0035] Its hydrogen spectrum is Figure 1 As shown, the carbon spectrum is Figure 2 shown.

[0036] Example 2

[0037] A method for preparing a fragrant raw material that highlights the sweet taste of cigarettes:

[0038] (1) In a 100 mL round-bottom flask, 1.44 g (10 mmol) of 1,4:3,6-dianhydro-D-pyranose glucose, 2.70 g (10 mmol) of heptadecanoic acid, 0.98 g (2 mmol) of scandium trifluoromethanesulfonate, 3.44 g (20 mmol) of p-toluenesulfonic acid, and 30 mL of toluene were added. The reaction system was stirred evenly and reacted at 120 °C for 12 h.

[0039] (2) After the reaction, dichloromethane and saturated sodium chloride solution (volume ratio 1:1) were added, and the organic phase was separated by extraction for 1-5 minutes and dried over anhydrous sodium sulfate. The reaction solvent was evaporated and the residue was purified by silica gel column chromatography (using petroleum ether and ethyl acetate as eluents, volume ratio 3:1-1:1, gradient elution) to obtain 2.85 g of 1,4:3,6-dianhydro-D-pyranose heptadecanoate, with a yield of 72.0%.

[0040] The structural formula of the target compound is shown in Formula II below:

[0041]

[0042] Example 3

[0043] A method for preparing a fragrant raw material that highlights the sweet taste of cigarettes:

[0044] (1) In a 100 mL round-bottom flask, 1.44 g (10 mmol) of 1,4:3,6-dianhydro-D-pyranose glucose, 2.84 g (10 mmol) of octadecanoic acid, 0.98 g (2 mmol) of scandium trifluoromethanesulfonate, 3.44 g (20 mmol) of p-toluenesulfonic acid, and 30 mL of toluene were added. The reaction system was stirred evenly and reacted at 160°C for 24 h.

[0045] (2) After the reaction, dichloromethane and saturated sodium chloride solution (volume ratio 1:1) were added, and the organic phase was separated by extraction for 1-5 minutes and dried over anhydrous sodium sulfate. The reaction solvent was evaporated and the residue was purified by silica gel column chromatography (using petroleum ether and ethyl acetate as eluents, volume ratio 3:1-1:1, gradient elution) to obtain 2.57 g of 1,4:3,6-dianhydro-D-pyranose octadecanoate, with a yield of 62.8%.

[0046] The structural formula of the target compound is shown in Formula III below:

[0047]

[0048] Example 4

[0049] A method for preparing a fragrant raw material that highlights the sweet taste of cigarettes:

[0050] (1) In a 100 mL round-bottom flask, 1.44 g (10 mmol) of 1,4:3,6-dianhydro-D-pyranose glucose, 2.98 g (10 mmol) of nonadecanoic acid, 0.49 g (1 mmol) of scandium trifluoromethanesulfonate, 3.44 g (20 mmol) of p-toluenesulfonic acid, and 30 mL of toluene were added. The reaction system was stirred evenly and reacted at 120°C for 24 h.

[0051] (2) After the reaction, dichloromethane and saturated sodium chloride solution (volume ratio 1:1) were added, and the organic phase was separated by extraction for 1-5 minutes and dried over anhydrous sodium sulfate. The reaction solvent was evaporated and the residue was purified by silica gel column chromatography (using petroleum ether and ethyl acetate as eluents, volume ratio 3:1-1:1, gradient elution) to obtain 3.19 g of 1,4:3,6-dianhydro-D-pyranose nonadecanoate, with a yield of 75.3%.

[0052] The structural formula of the target compound is shown in Formula IV below:

[0053]

[0054] Flavoring Performance Test: Weigh compounds 1-4 and dilute them with ethanol to a 1% solution for later use. Weigh 50g of unflavored blank cigarette cut tobacco and spread it evenly on a clean tray. Spray the compound ethanol solution evenly on the cut tobacco to produce cigarette cut tobacco with a compound-to-tobacco ratio of 1ppm, 10ppm, 50ppm, and 100ppm. Seal the cut tobacco and let it sit for 4 hours. Dry it in a 50°C oven and humidify it with distilled water to a standard moisture content (12%). Roll it into standard cigarettes and equilibrate them to a moisture content of 60%±2% and a temperature of 22±1°C for 48 hours before smoking. A blank cigarette was used as the control, and the control was equilibrated under the same temperature and humidity conditions for 48 hours.

[0055] Table 1 Sensory evaluation results

[0056]

[0057] It can be seen from Table 1 that compounds 1 to 4 have the ability to significantly improve and modify the aroma of cigarettes, imparting sweet ester aroma and sweet flavor to cigarettes, and the appropriate dosage is 1-50 ppm.

[0058] Although the present invention has been disclosed above by way of embodiments, they are not intended to limit the present invention. Any person skilled in the art may make various choices and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention is defined by the claims and their equivalents.

Claims

1. A flavoring material that highlights the sweetness of cigarettes, characterized in that: The structural formula of the fragrant raw material is as follows: 。 2. The method for preparing a fragrant raw material that highlights the sweet taste of cigarettes according to claim 1, characterized in that: The following steps are involved: (1) In a reaction flask, first add the raw material 1,4:3,6-dianhydro-D-pyranose glucose, acid, catalyst, additive and organic solvent, stir the reaction system evenly, and react at 120-200°C for 12-24 hours; the catalyst is scandium trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate or lanthanum trifluoromethanesulfonate, the additive is one or more of benzenesulfonic acid, p-toluenesulfonic acid or p-methoxybenzenesulfonic acid; the acid is hexadecanoic acid, heptadecanoic acid, octadecanoic acid or nonadecanoic acid; the organic solvent is toluene; (2) After the reaction is completed, dichloromethane and saturated sodium chloride solution are added, and the organic phase is extracted and separated, and then dried over anhydrous sodium sulfate. The reaction solvent is evaporated, and the residue is purified by silica gel column chromatography to obtain the target product.

3. The method for preparing a fragrant raw material that highlights the sweet taste of cigarettes according to claim 2, characterized in that: In step (1), the molar ratio of the raw material 1,4:3,6-dianhydro-D-pyranose, acid, catalyst and additive is 1:(1.0-3.0):(0.1-0.5):(0.5-3.0).

4. The method for preparing a fragrant raw material for highlighting the sweet taste of cigarettes according to claim 2, characterized in that: In step (2), the volume ratio of dichloromethane and saturated sodium chloride solution to the solution of step (1) is 1:1-1:2, the volume ratio of dichloromethane and saturated sodium chloride is 1:1, and the extraction time is 1-5 minutes.

5. The method for preparing a fragrant raw material for highlighting the sweet taste of cigarettes according to claim 2, characterized in that: In step (2), silica gel column chromatography uses petroleum ether and ethyl acetate as eluents in a volume ratio of 3:1-1:1, and gradient elution.

6. Use of the aroma raw material for highlighting the sweetness of cigarettes according to claim 1 or the aroma raw material for highlighting the sweetness of cigarettes prepared by the preparation method according to any one of claims 2 to 5 in cigarettes.

7. The use according to claim 6, characterized in that The aromatic raw material that highlights the sweet taste of cigarettes is used as a fragrance in cigarettes, and the added amount is 1 to 50 ppm based on the mass of the cigarette shreds.

8. A cigarette, characterized in that: The cigarette contains the aroma raw material for highlighting the sweetness of cigarettes according to claim 1 or the aroma raw material for highlighting the sweetness of cigarettes prepared by the preparation method according to any one of claims 2 to 5.

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