Fragrance material capable of highlighting sweetness characteristic of cigarette as well as preparation method and application of fragrance material

Abstract

The invention discloses a fragrant raw material capable of highlighting the sweet taste characteristic of cigarettes and a preparation method and application of the fragrant raw material, the structural formula of the fragrant raw material is as follows: # imgabs0 #, and the preparation method of the fragrant raw material comprises the following steps: in a reaction flask, adding raw materials 1, 4: 3, 6-dianhydro-D-glucopyranose, acid, a catalyst, an additive and an organic solvent, uniformly stirring a reaction system, and reacting for 12-24 hours at 120-200 DEG C; and after the reaction is finished, adding dichloromethane and a saturated sodium chloride solution, extracting and separating to obtain an organic phase, drying by using anhydrous sodium sulfate, evaporating to remove a reaction solvent, and purifying residues by using silica gel column chromatography to obtain a target product. According to the invention, 1, 4: 3, 6-dianhydro-D-glucopyranose is used as an initial raw material to synthesize a series of anhydrosugar long-chain ester compounds. After being added into cigarettes, the spice can enrich cigarette aroma, endow the cigarettes with ester sweet aroma and scorch aroma, and improve aftertaste comfort.

Description

Technical Field

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

[0002] 1,4:3,6-dianhydro-D-pyranose glucose is commonly found in cigarette smoke and sugar decomposition products. It is a pyran compound generated 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 highlighting the sweet taste characteristics of cigarettes, and a preparation method and application thereof, and 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 characteristics 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, additive and organic solvent, stir the reaction system evenly, and react at 120-200° C. for 12-24 hours;

[0012] (2) After the reaction is completed, dichloromethane and saturated sodium chloride solution are added, and the organic phase is extracted and separated and 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.

[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 in 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 characteristics 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 of the mass of cigarette shreds.

[0020] A cigarette containing flavoring materials that accentuate the sweet flavor characteristics of the cigarette.

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

[0022] The present invention uses 1,4:3,6-dianhydro-D-pyranose glucose as the starting material to synthesize a series of anhydrosugar long-chain ester compounds. The flavor is added to cigarettes to enrich the aroma of cigarettes, give the cigarettes esters sweet and caramel aromas, and improve the comfort of the aftertaste. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The accompanying drawings, which are incorporated in and constitute a part of the 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 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 unless otherwise specifically stated.

[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 characteristics of cigarettes:

[0030] (1) In a 100 mL round-bottom flask, 1.44 g (10 mmol) of 1,4:3,6-dianhydro-D-pyranose, 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 and dried over anhydrous sodium sulfate for 1-5 min. 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 characteristics of cigarettes:

[0038] (1) In a 100 mL round-bottom flask, 1.44 g (10 mmol) of 1,4:3,6-dianhydro-D-pyranose, 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 after extraction for 1-5 min 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 characteristics of cigarettes:

[0044] (1) In a 100 mL round-bottom flask, 1.44 g (10 mmol) of 1,4:3,6-dianhydro-D-pyranose, 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 and dried over anhydrous sodium sulfate for 1-5 min. 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 characteristics 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 and dried over anhydrous sodium sulfate for 1-5 min. 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] Flavor performance test: Weigh compounds 1 to 4 and dilute them with ethanol to a 1% solution for later use. Weigh 50g of blank cigarette shreds without flavoring or adding materials, spread them evenly on a clean tray, and spray the ethanol solution of the compound evenly on the shreds to obtain shredded cigarettes with a compound to shredded ratio of 1ppm, 10ppm, 50ppm and 100ppm. Seal and place for 4 hours, put in a 50℃ oven to dry, humidify with distilled water to the standard moisture (12%), roll into standard cigarettes, balance the moisture (humidity 60%±2%, temperature 22±1℃) for 48 hours, and then evaluate. The control sample is a blank cigarette, and the control sample is balanced for 48 hours under the same temperature and humidity conditions.

[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, giving the cigarettes ester sweet and sweet aromas, and the appropriate dosage is 1-50 ppm.

[0058] Although the present invention has been disclosed as above by the embodiments, it is 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 protection scope of the present invention is limited by the claims and their equivalents.

Claims

1. A flavoring material that highlights the sweet taste of cigarettes, characterized in that: The structural formula of the fragrant raw material is as follows:

2. The method for preparing the aroma raw material with outstanding sweet taste characteristics of cigarette 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, acid, catalyst, additive and organic solvent, stir the reaction system evenly, and react at 120-200° C. for 12-24 hours; (2) After the reaction is completed, dichloromethane and saturated sodium chloride solution are added, and the organic phase is extracted and separated and 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 the aroma raw material with prominent sweet taste characteristics of cigarette according to claim 2, characterized in that: 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.

4. The method for preparing the aroma raw material with outstanding sweet taste characteristics of cigarette according to claim 2, characterized in that: 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.

5. The method for preparing the aroma raw material with prominent sweet taste characteristics of cigarette 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).

6. The method for preparing the aroma raw material with prominent sweet taste characteristics of cigarette according to claim 2, characterized in that: In step (2), the volume ratio of dichloromethane and saturated sodium chloride solution to the solution in 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.

7. The method for preparing a fragrant raw material with a prominent sweet taste characteristic of cigarettes according to claim 2, characterized in that: 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.

8. Use of the aroma raw material for highlighting the sweet taste characteristics of cigarettes according to claim 1 or the aroma raw material for highlighting the sweet taste characteristics of cigarettes prepared by the preparation method according to any one of claims 2 to 7 in cigarettes.

9. The use according to claim 8, characterized in that: The aromatic raw material that highlights the sweet taste characteristics of cigarettes is used as a flavoring in cigarettes, and the added amount is 1 to 50 ppm of the mass of cigarette shreds.

10. A cigarette, characterized in that: The cigarette contains the aroma raw material for highlighting the sweet taste characteristics of the cigarette according to claim 1 or the aroma raw material for highlighting the sweet taste characteristics of the cigarette prepared by the preparation method according to any one of claims 2-7.

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