Carboxymethylated dehydrated sugar as well as preparation method and application thereof

Abstract

The invention discloses carboxymethylated dehydrated sugar and a preparation method and application thereof.The preparation method of the carboxymethylated dehydrated sugar comprises the following steps that raw materials 1, 4: 3, 6-dianhydro-D-glucopyranose, a diazomethane diethyl ether solution, a catalyst, alkali and dichloromethane are sequentially added into a high-pressure reaction kettle, the mixture is heated to 80-90 DEG C, the mixture is heated to 80-90 DEG C, and the mixture is cooled to room temperature to obtain the carboxymethylated dehydrated sugar with the content of 1, 4: 3, 6-dianhydro-D-glucopyranose and the content of 1, 4: 3, 6-dianhydro-D-glucopyranose. Replacing air in the reaction kettle with carbon dioxide; after uniformly stirring, heating and reacting for 10 hours at the temperature of 100-150 DEG C, then cooling the reaction kettle to room temperature, adding excessive diluted hydrochloric acid into the reaction system, and continuously stirring and reacting for 1 hour; and after the reaction is finished, extracting and separating to obtain an organic phase, drying with anhydrous sodium sulfate, evaporating under reduced pressure to remove the solvent, and performing column chromatography separation on solid residues to obtain carboxymethylated dehydrated sugar. According to the technical scheme, 1, 4: 3, 6-dianhydro-D-glucopyranose is used as an initial raw material to synthesize the carboxymethylated dehydrated sugar. When the fragrant raw material is added into the cigarette, the sweet feeling of the oral cavity can be improved, the smoke permeability and the fine degree are improved, and the aftertaste comfort is improved.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a carboxymethylated dehydrated sugar 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] Volatile organic acids can adjust the pH of tobacco, improve the quality of smoking, make the taste mellower, increase the smoke concentration, improve the mellowness of the smoke, and play a role in acid-base balance in the smoke.

[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 carboxymethylated dehydrated sugar and a preparation method and application thereof. The preparation method has simple operation, high yield and is easy for large-scale production.

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

[0007] A carboxymethylated anhydrosugar, the structural formula is as follows:

[0008]

[0009] A method for preparing carboxymethylated dehydrated sugar comprises the following steps:

[0010]

[0011] (1) In a high-pressure reactor, raw materials 1,4:3,6-dianhydro-D-pyranose, diazomethane ether solution, catalyst, alkali and dichloromethane are added in sequence, and the air in the reactor is replaced with carbon dioxide;

[0012] (2) After the reaction system is stirred evenly, the reaction is heated at 100-150°C for 10 hours, and then the reactor is cooled to room temperature, and excess dilute hydrochloric acid is added to the reaction system, and the stirring reaction is continued for 1 hour;

[0013] (3) After the reaction is completed, the organic phase is separated by extraction and dried over anhydrous sodium sulfate, the solvent is evaporated under reduced pressure, and the solid residue is separated by column chromatography to obtain carboxymethylated dehydrated sugar.

[0014] Preferably, in the above technical solution, in step (1), the catalyst is ferric chloride, ruthenium chloride or cobalt dichloride, and the base is lithium tert-butoxide, butyl lithium or potassium tert-butoxide.

[0015] Preferably, in the above technical solution, in step (1), the molar ratio of the raw material 1,4:3,6-dianhydro-D-pyranose glucose, the catalyst and the base is 1:(0.2-1.0):(1.0-5.0).

[0016] Preferably, in the above technical solution, in step (1), the pressure of carbon dioxide in the reactor is 3.0 to 5.0 MPa.

[0017] Preferably, in the above technical solution, in step (2), the extraction time is: 1-5 min.

[0018] Preferably, in the above technical solution, in step (3), 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.

[0019] Application of carboxymethylated dehydrated sugar in cigarettes.

[0020] Preferably, in the above technical solution, the carboxymethylated dehydrated sugar is applied to cigarettes as a flavoring agent, and the added amount is 10 to 100 ppm based on the mass of the cigarette tobacco.

[0021] A cigarette comprising carboxymethylated anhydrosugar.

[0022] The above technical solution of the present invention has the following beneficial effects:

[0023] This technical solution uses 1,4:3,6-dianhydro-D-pyranose glucose as the starting material to synthesize carboxymethylated anhydrosugar. This aroma raw material can be added to cigarettes to increase the sweetness of the mouth, increase the smoke permeability and fineness, and improve the comfort of the aftertaste. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] 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.

[0025] Figure 1 The compound of Example 1 1 H spectrum.

[0026] Figure 2 The compound of Example 1 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] (1) In a 500 mL autoclave, 1.44 g (10 mmol) of 1,4:3,6-dianhydro-D-pyranose, 5.0 g of diazomethane ether solution, 0.32 g (2 mmol) of ferric chloride, 2.40 g (30 mmol) of lithium tert-butoxide, and 50 mL of dichloromethane were added in sequence, and then the air in the autoclave was replaced with carbon dioxide. The carbon dioxide pressure in the autoclave was 5.0 MPa.

[0031] (2) After the reaction system is stirred evenly, it is heated at 100°C for 10 hours, and then the reactor is cooled to room temperature, and excess dilute hydrochloric acid is added to the reaction system, and the stirring reaction is continued for 1 hour;

[0032] (3) After the reaction, the organic phase was separated by extraction for 1-5 min and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the solid residue was separated by column chromatography (using petroleum ether and ethyl acetate as eluents, volume ratio 3:1-1:1, gradient elution) to obtain 1.70 g of carboxymethylated anhydrosugar, with a yield of 84.2%.

[0033] The structural formula of carboxymethylated anhydrosugar is as follows:

[0034]

[0035] Compound structure characterization:

[0036] 1 H NMR (400 MHz, CDCl 3 )δ5.63(s,1H),5.19(dd,J=4.7,3.3Hz,1H),4.30(d,J=4.0Hz,1H),4.26~4.13(m,3H),4.02(d,J=10.7Hz,1H),3.95(d,J=2.4Hz,1H),3.60(s,1H); 13 C NMR (400MHz, CDCl 3 )δ172.81,99.53,86.69,80.34,79.49,75.86,71.78,66.28; MS(ESI):m / z 203.02[M+H +].

[0037] Flavor performance test:

[0038] Weigh a certain amount of carboxymethylated glucose, 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 carboxymethylated glucose on the shredded tobacco to obtain shredded cigarettes with a specific gravity of 5ppm, 10ppm, 50ppm, 100ppm and 200ppm to the shredded tobacco, seal and place for 4h, 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 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.

[0039] Table 1 Sensory evaluation results

[0040]

[0041] It can be seen from Table 1 that carboxymethylated dehydrated sugar has the effects of increasing sweetness, softening smoke, reducing irritation, and making the aftertaste clean and comfortable. The optimal dosage is 10-100ppm.

[0042] 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 defined by the claims and their equivalents.

Claims

1. A carboxymethylated anhydrosugar, characterized in that: The structural formula of the carboxymethylated anhydrosugar is as follows:

2. The method for preparing carboxymethylated dehydrated sugar according to claim 1, wherein The following steps are involved: (1) In a high-pressure reactor, raw materials 1,4:3,6-dianhydro-D-pyranose, diazomethane ether solution, catalyst, alkali and dichloromethane are added in sequence, and the air in the reactor is replaced with carbon dioxide; (2) After the reaction system is stirred evenly, the reaction is heated at 100-150°C for 10 hours, and then the reactor is cooled to room temperature, and excess dilute hydrochloric acid is added to the reaction system, and the stirring reaction is continued for 1 hour; (3) After the reaction is completed, the organic phase is separated by extraction and dried over anhydrous sodium sulfate, the solvent is evaporated under reduced pressure, and the solid residue is separated by column chromatography to obtain carboxymethylated dehydrated sugar.

3. The method for preparing carboxymethylated dehydrated sugar according to claim 2, characterized in that: In step (1), the catalyst is ferric chloride, ruthenium chloride or cobalt dichloride, and the base is lithium tert-butoxide, butyl lithium or potassium tert-butoxide.

4. The method for preparing carboxymethylated dehydrated sugar according to claim 2, wherein: In step (1), the molar ratio of the raw material 1,4:3,6-dianhydro-D-pyranose, the catalyst and the base is 1:(0.2-1.0):(1.0-5.0).

5. The method for preparing carboxymethylated dehydrated sugar according to claim 2, characterized in that: In step (1), the pressure of carbon dioxide in the reactor is 3.0 to 5.0 MPa.

6. The method for preparing carboxymethylated dehydrated sugar according to claim 2, characterized in that: In step (3), the extraction time is: 1-5min.

7. The method for preparing carboxymethylated dehydrated sugar according to claim 2, characterized in that: In step (3), 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 carboxymethylated dehydrated sugar according to claim 1 or the carboxymethylated dehydrated sugar 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 carboxymethylated dehydrated sugar is used as a flavor in cigarettes, and the added amount is 10 to 100 ppm of the mass of the cigarette shreds.

10. A cigarette, characterized in that: The cigarette contains the carboxymethylated dehydrated sugar according to claim 1 or the carboxymethylated dehydrated sugar prepared by the preparation method according to any one of claims 2 to 7.

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