1, 4: 3, 6-dianhydro-D-glucopyranose carbonate as well as preparation method and application thereof

Abstract

The invention discloses 1, 4: 3, 6-dianhydro-D-glucopyranose carbonate, which has the following structural formula: # imgabs0 #, in which R is phenyl or methyl. The preparation method of the 1, 4: 3, 6-dianhydro-D-glucopyranose carbonic ester comprises the following steps: adding raw materials 1, 4: 3, 6-dianhydro-D-glucopyranose and alcohol into a high-pressure reaction kettle, then sequentially adding a catalyst, a ligand and methylbenzene, replacing air in the reaction kettle with carbon dioxide, increasing the pressure of the carbon dioxide in a reaction system to 5.0-10.0 MPa, carrying out heat preservation for 2-3 hours, and carrying out heat preservation for 2-3 hours, so as to obtain the 1, 4: 3, 6-dianhydro-D-glucopyranose carbonic ester. Then heating and reacting at 150 to 200 DEG C for 24 hours; after the reaction is finished, cooling a reaction system to normal temperature and normal pressure, performing extraction separation on reaction liquid to obtain an organic phase, drying with anhydrous sodium sulfate, performing reduced-pressure evaporation to remove the solvent, and performing column chromatography separation on solid residues to obtain a target product. According to the present invention, the 1, 4: 3, 6-dianhydro-D-glucopyranose carbonate is synthesized by using the 1, 4: 3, 6-dianhydro-D-glucopyranose as the starting material; when the spice is added into the cigarette, the cigarette fragrance can be enriched, the smoke permeability and the fine degree are improved, and the potential application value is achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and in particular to 1,4:3,6-dianhydro-D-pyranose carbonate and a preparation method and application thereof. Background Art

[0002] 1,4:3,6-dianhydro-D-pyranose glucose (DAGP) is commonly found in cigarette smoke and sugar decomposition products. It is a pyran compound generated by sugar degradation and has the characteristics of volatility, fat solubility and water solubility. After being added to cigarettes, it has problems such as easy volatility and short fragrance retention time.

[0003] Therefore, the DAGP compound can be structurally modified through chemical synthesis to synthesize a series of tobacco flavorings with stable flavoring properties and outstanding effects. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a 1,4:3,6-dianhydro-D-pyranose glucose carbonate and a preparation method and application thereof, which are simple to operate, high in yield and easy to mass produce.

[0005] The technical problem to be solved by the present invention is achieved through the following technical solutions:

[0006] A 1,4:3,6-dianhydro-D-pyranose carbonate, the structural formula of which is as follows:

[0007]

[0008] Wherein, R is phenyl or methyl.

[0009] A method for preparing 1,4:3,6-dianhydro-D-pyranose glucose carbonate comprises the following steps:

[0010]

[0011] (1) Adding raw materials 1,4:3,6-dianhydro-D-pyranose glucose and alcohol to a high-pressure reactor, and then adding a catalyst, a ligand and toluene in sequence, replacing the air in the reactor with carbon dioxide, and increasing the pressure of carbon dioxide in the reaction system to 5.0-10.0 MPa, and then heating the reaction at 150-200° C. for 24 hours;

[0012] (2) After the reaction is completed, the reaction system is cooled to room temperature and pressure, the reaction solution is separated by extraction to obtain an organic phase, which is dried over anhydrous sodium sulfate, the solvent is evaporated under reduced pressure, and the solid residue is separated by column chromatography to obtain the target product.

[0013] Preferably, in the above technical solution, in step (1), the catalyst is palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium or bis(triphenylphosphine)palladium chloride; and the ligand is 1,2-bis(diphenylphosphine)ethane, 1,2-bis(diphenylphosphine)propane or 1,2-bis(diphenylphosphine)butane.

[0014] Preferably, in the above technical scheme, in step (1), the molar ratio of the raw material 1,4:3,6-dianhydro-D-pyranose, alcohol, catalyst and ligand is 1:(1.0-5.0):(0.05-0.2):(0.1-0.5).

[0015] Preferably, in the above technical solution, in step (2), the extraction time is: 1-5 min.

[0016] 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.

[0017] Application of 1,4:3,6-dianhydro-D-pyranose carbonate in cigarettes.

[0018] Preferably, in the above technical solution, the 1,4:3,6-dianhydro-D-pyranose glucose carbonate is used as a flavoring in cigarettes, and the added amount is 1 to 50 ppm based on the mass of the cigarette tobacco.

[0019] A cigarette comprising 1,4:3,6-dianhydro-D-pyranose carbonate.

[0020] The above technical solution of the present invention has the following beneficial effects:

[0021] The present application uses 1,4:3,6-dianhydro-D-pyranose glucose as a starting material to synthesize a 1,4:3,6-dianhydro-D-pyranose glucose carbonate. The flavor can be added to cigarettes to enrich the aroma of the cigarette, increase the permeability and fineness of the smoke, and has potential application value. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] 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.

[0023] Figure 1 The compound of Example 1 1 H spectrum.

[0024] Figure 2 The compound of Example 1 13 C spectrum.

[0025] Figure 3 The compound of Example 21 H spectrum.

[0026] Figure 4 The compound of Example 2 13 C spectrum. DETAILED DESCRIPTION

[0027] 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.

[0028] 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.

[0029] Example 1

[0030] A method for preparing 1,4:3,6-dianhydro-D-pyranose glucose carbonate:

[0031] (1) In a 500 mL autoclave, 1.44 g (10 mmol) of 1,4:3,6-dianhydro-D-pyranose, 1.60 g (50 mmol) of methanol, 0.22 g (1 mmol) of palladium acetate, 0.82 g (2 mmol) of 1,2-bis(diphenylphosphino)propane and 50 mL of toluene were added in sequence, and then the air in the autoclave was replaced with carbon dioxide. The carbon dioxide pressure in the autoclave was 10.0 MPa.

[0032] (2) After the reaction system is stirred evenly, it is heated at 150°C for 24 hours.

[0033] (3) After the reaction, the organic phase was separated by extraction and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the solid residue was separated by column chromatography to obtain 1.90 g of 1,4:3,6-dianhydro-D-pyranose glucose carbonate methyl ester with a yield of 94.2%.

[0034] The structural formula is as follows:

[0035]

[0036] Structural characterization of compounds:

[0037] 1H NMR (400MHz, CDCl3) δ5.61(d,J=0.8Hz,1H),5.20(dd,J=4.7,3.3Hz,1H),4.50(s,1H),4.31(dd,J=4.7 ,0.9Hz,1H),4.25(t,J=2.8Hz,1H),4.08(d,J=10.8Hz,1H),3.96(dd,J=10.8,2.4Hz,1H),3.81(s,3H); 13 C NMR (101MHz, CDCl3) δ154.56,98.77,82.31,80.18,79.59,75.93,71.79,55.21.

[0038] Example 2

[0039] A method for preparing 1,4:3,6-dianhydro-D-pyranose glucose carbonate:

[0040] (1) In a 500 mL autoclave, 1.44 g (10 mmol) of 1,4:3,6-dianhydro-D-pyranose, 5.40 g (50 mmol) of benzyl alcohol, 0.22 g (1 mmol) of palladium acetate, 0.82 g (2 mmol) of 1,2-bis(diphenylphosphino)propane and 50 mL of toluene were added in sequence, and then the air in the autoclave was replaced with carbon dioxide. The carbon dioxide pressure in the autoclave was 10.0 MPa.

[0041] (2) After the reaction system is stirred evenly, it is heated at 150°C for 24 hours.

[0042] (3) After the reaction, the organic phase was separated by extraction and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the solid residue was separated by column chromatography to obtain 2.51 g of 1,4:3,6-dianhydro-D-pyranose benzyl carbonate, with a yield of 90.5%.

[0043] The structural formula is as follows:

[0044]

[0045] Structural characterization of compounds:

[0046] 1H NMR (400MHz, CDCl3) δ8.03(dd,J=8.2,1.0Hz,2H),7.58(t,J=7.4Hz,1H),7.44(t,J=7.8Hz,2H),5.68(s,1H),5.25(dd,J=4. 6,3.3Hz,1H),4.83(s,1H),4.44–4.40(m,1H),4.29(t,J=2.8Hz,1H),4.14(d,J=10.8Hz,1H),4.01(dd,J=10.8,2.5Hz,1H); 13 C NMR (400MHz, CDCl3) δ165.42,133.44,129.80,129.22,128.44,99.16,80.62,80.07,79.66,75.99,71.87.

[0047] Flavor performance test:

[0048] Weigh a certain amount of 1,4:3,6-dianhydro-D-pyranose glucose carbonate methyl ester, dilute it with ethanol to a 1% solution, and set aside. Weigh 100g of blank cigarette shreds without flavoring or adding materials, evenly spread them on a clean tray, and evenly spray the ethanol solution of the compound on the shreds to obtain shredded cigarettes with a compound to shreds ratio of 0.5ppm, 1ppm, 10ppm, 50ppm and 100ppm, seal and place for 4h, put in a 50℃ oven to dry, humidify with distilled water to standard moisture (12%), roll into standard cigarettes, balance moisture (humidity 60%±2%, temperature 22±1℃) for 48h before evaluation. The control sample is a blank cigarette, and the control sample is balanced for 48h under the same temperature and humidity conditions.

[0049] Table 1 Sensory evaluation results

[0050]

[0051] It can be seen from Table 1 that dehydrosugar carbonate has the effects of significantly improving and modifying the aroma of cigarettes, enriching the aroma of cigarettes, reducing irritation, improving the taste of smoking, and making the aftertaste clean and comfortable. The dosage is 1-50ppm.

[0052] 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 1,4:3,6-dianhydro-D-pyranose carbonate, characterized in that: The structural formula of the 1,4:3,6-dianhydro-D-pyranose carbonate is as follows: Wherein, R is phenyl or methyl.

2. The method for preparing 1,4:3,6-dianhydro-D-pyranose glucose carbonate according to claim 1, characterized in that: The following steps are involved: (1) Adding raw materials 1,4:3,6-dianhydro-D-pyranose glucose and alcohol to a high-pressure reactor, and then adding a catalyst, a ligand and toluene in sequence, replacing the air in the reactor with carbon dioxide, and increasing the pressure of carbon dioxide in the reaction system to 5.0-10.0 MPa, and then heating the reaction at 150-200° C. for 24 hours; (2) After the reaction is completed, the reaction system is cooled to room temperature and pressure, the reaction solution is separated by extraction to obtain an organic phase, which is dried over anhydrous sodium sulfate, the solvent is evaporated under reduced pressure, and the solid residue is separated by column chromatography to obtain the target product.

3. The method for preparing 1,4:3,6-dianhydro-D-pyranose glucose carbonate according to claim 2, characterized in that: In step (1), the catalyst is palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium or bis(triphenylphosphine)palladium chloride; and the ligand is 1,2-bis(diphenylphosphine)ethane, 1,2-bis(diphenylphosphine)propane or 1,2-bis(diphenylphosphine)butane.

4. The method for preparing 1,4:3,6-dianhydro-D-pyranose glucose carbonate according to claim 2, characterized in that: In step (1), the molar ratio of the raw material 1,4:3,6-dianhydro-D-pyranose, alcohol, catalyst and ligand is 1:(1.0-5.0):(0.05-0.2):(0.1-0.5).

5. The method for preparing 1,4:3,6-dianhydro-D-pyranose glucose carbonate according to claim 2, characterized in that: In step (2), the extraction time is: 1-5min.

6. The method for preparing 1,4:3,6-dianhydro-D-pyranose glucose carbonate 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.

7. Use of the 1,4:3,6-dianhydro-D-pyranose glucose carbonate according to claim 1 or the 1,4:3,6-dianhydro-D-pyranose glucose carbonate prepared according to any one of the preparation methods according to claims 2 to 6 in cigarettes.

8. The use according to claim 7, characterized in that: The 1,4:3,6-dianhydro-D-pyranose carbonate is used as a flavor in cigarettes, and the added amount is 1 to 50 ppm of the mass of the cigarette shreds.

9. A cigarette, characterized in that: The cigarette contains the 1,4:3,6-dianhydro-D-pyranose glucose carbonate according to claim 1 or the 1,4:3,6-dianhydro-D-pyranose glucose carbonate prepared by the preparation method according to any one of claims 2-6.

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