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

Abstract

The invention discloses 1, 4: 3, 6-dianhydro-D-glucopyranose oxalic acid diester as well as a preparation method and application thereof, the structural formula of the 1, 4: 3, 6-dianhydro-D-glucopyranose oxalic acid diester is as follows: # imgabs 0 #, and the preparation method of the 1, 4: 3, 6-dianhydro-D-glucopyranose oxalic acid diester comprises the following steps: sequentially adding 1, 4: 3, 6-dianhydro-D-glucopyranose oxalic acid diester into a reaction kettle, reacting at the temperature of 60-80 DEG C for 2-3 hours, and then adding a catalyst, a catalyst, a catalyst and a catalyst to obtain the 1, 4: 3, 6-dianhydro-D-glucopyranose oxalic acid diester. The method comprises the following steps: adding 2, 6-dianhydro-D-glucopyranose, ethylene glycol and acid into a reaction kettle, replacing air in the reaction kettle with oxygen, heating to 100-160 DEG C, and reacting for 10-16 hours; and after the reaction is finished, adding a saturated sodium bicarbonate solution and dichloromethane for washing, carrying out extraction separation to obtain an organic phase, drying with anhydrous Na2SO4, carrying out reduced pressure distillation to remove the solvent, and carrying out silica gel column chromatography separation on a crude product to obtain the 1, 4: 3, 6-dianhydro-D-glucopyranose oxalic acid diester. According to the present invention, 1, 4: 3, 6-dianhydro-D-glucopyranose is adopted as the starting material to synthesize the 1, 4: 3, 6-dianhydro-D-glucopyranose oxalic acid diester; after being added into cigarettes, the aroma raw material can enrich cigarette aroma, soften smoke and improve aftertaste comfort, and has potential application value.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to 1,4:3,6-dianhydro-D-pyranose glucoside oxalate 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, which limits its use as a flavoring.

[0003] Therefore, the structure of DAGP compounds can be 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 glucoside oxalate 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 glucoside oxalate, the structural formula of which is as follows:

[0007]

[0008] A method for preparing 1,4:3,6-dianhydro-D-pyranose glucoside oxalate comprises the following steps:

[0009]

[0010] (1) Add 1,4:3,6-dianhydro-D-pyranose glucose, ethylene glycol and acid to a reaction kettle in sequence, replace the air in the reaction kettle with oxygen, and heat to 100-160° C. for reaction for 10-16 hours;

[0011] (2) After the reaction is completed, a saturated sodium bicarbonate solution and dichloromethane are added for washing, and the organic phase is separated by extraction and dried over anhydrous Na2SO4. The solvent is evaporated under reduced pressure, and the crude product is separated by silica gel column chromatography to obtain 1,4:3,6-dianhydro-D-pyranose glucoside oxalate.

[0012] Preferably, in the above technical solution, in step (1), the acid is concentrated sulfuric acid, concentrated nitric acid or concentrated hydrochloric acid.

[0013] Preferably, in the above technical solution, in step (1), the pressure of oxygen in the reactor is 5.0 to 10.0 MPa.

[0014] Preferably, in the above technical solution, in step (1), the molar ratio of 1,4:3,6-dianhydro-D-pyranose, ethylene glycol and acid is 1:(1-2):(0.05-0.1).

[0015] Preferably, in the above technical solution, in step (2), the extraction time is: 1-5 min; the silica gel column chromatography uses petroleum ether and ethyl acetate as eluents, with a volume ratio of 3:1-1:1, and gradient elution.

[0016] Application of 1,4:3,6-dianhydro-D-pyranose glucoside oxalate in cigarettes.

[0017] Preferably, in the above technical solution, the 1,4:3,6-dianhydro-D-pyranose glucoside oxalate is used as a flavoring in cigarettes, and the added amount is 5 to 100 ppm based on the mass of the cigarette tobacco.

[0018] A cigarette contains 1,4:3,6-dianhydro-D-pyranoglucopyranose oxalate diester.

[0019] The above technical solution of the present invention has the following beneficial effects:

[0020] The present invention uses 1,4:3,6-dianhydro-D-pyranose glucose as a starting material to synthesize 1,4:3,6-dianhydro-D-pyranose glucose oxalate. The aroma raw material can be added to cigarettes to enrich the aroma, soften the smoke, and improve the comfort of the aftertaste, and has potential application value. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] 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.

[0022] Figure 1 The compound of Example 1 1 H spectrum.

[0023] Figure 2 The compound of Example 1 13 C spectrum. DETAILED DESCRIPTION

[0024] 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.

[0025] 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.

[0026] Example 1

[0027] A method for preparing 1,4:3,6-dianhydro-D-pyranose glucoside oxalate:

[0028] (1) In a 100 mL autoclave, 1.44 g (10 mmol) of 1,4:3,6-dianhydro-D-pyranose, 6.02 g (100 mmol) of ethylene glycol, and 1.96 g (20 mmol) of sulfuric acid were added in sequence, and then the air in the autoclave was replaced with oxygen. The carbon dioxide pressure in the autoclave was 8.0 MPa.

[0029] (2) After the reaction system is stirred evenly, it is heated at 150°C for 10 h.

[0030] (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 (silica gel column chromatography using petroleum ether and ethyl acetate as eluents, volume ratio 3:1-1:1, gradient elution) to obtain 1.14 g of 1,4:3,6-dianhydro-D-pyranose glucoside oxalate, with a yield of 72.6%.

[0031] The structural formula of 1,4:3,6-dianhydro-D-pyranose glucoside oxalate is as follows:

[0032]

[0033] Structural characterization of compounds:

[0034] 1 H NMR (400MHz, CDCl3) δ5.63 (d, J=0.9Hz, 1H), 5.24 (dd, J=4.7, 3.3Hz, 1H), 4.70 (s, 1H), 4.38 (dd, J=4.8,1.0Hz,1H),4.28(t,J=2.7Hz,1H),4.10(d,J=10.8Hz,1H),3.98(dd,J=10.8,2.4Hz,1H); 13 C NMR (400MHz, CDCl3) δ155.92,98.21,81.68,79.97,79.72,76.02,71.79; MS (ESI): m / z 343.06[M+H + ].

[0035] Flavor performance test:

[0036] Weigh a certain amount of 1,4:3,6-dianhydro-D-pyranose glucoside oxalate, 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 1ppm, 5ppm, 25ppm, 100ppm and 200ppm, 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.

[0037] Table 1 Sensory evaluation results

[0038]

[0039] It can be seen from Table 1 that dehydrated sugar oxalate diester has the effect of significantly improving and modifying the aroma of cigarettes, reducing irritation, improving the taste of smoking, and making the aftertaste clean and comfortable. The appropriate dosage is 5-100ppm.

[0040] 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 glucoside oxalate, characterized in that: The structural formula of the 1,4:3,6-dianhydro-D-pyranose glucoside oxalate is as follows:

2. The method for preparing 1,4:3,6-dianhydro-D-pyranose glucoside oxalate according to claim 1, characterized in that: The following steps are involved: (1) Add 1,4:3,6-dianhydro-D-pyranose glucose, ethylene glycol and acid to a reaction kettle in sequence, replace the air in the reaction kettle with oxygen, and heat to 100-160° C. for reaction for 10-16 hours; (2) After the reaction is completed, a saturated sodium bicarbonate solution and dichloromethane are added for washing, and the organic phase is separated by extraction and dried over anhydrous Na2SO4. The solvent is evaporated under reduced pressure, and the crude product is separated by silica gel column chromatography to obtain 1,4:3,6-dianhydro-D-pyranose glucoside oxalate.

3. The method for preparing 1,4:3,6-dianhydro-D-pyranose glucoside oxalate according to claim 2, characterized in that: In step (1), the acid is concentrated sulfuric acid, concentrated nitric acid or concentrated hydrochloric acid.

4. The method for preparing 1,4:3,6-dianhydro-D-pyranose glucoside oxalate according to claim 2, characterized in that: In step (1), the molar ratio of 1,4:3,6-dianhydro-D-pyranose, ethylene glycol and acid is 1:(1-2):(0.05-0.1).

5. The method for preparing 1,4:3,6-dianhydro-D-pyranose glucoside oxalate according to claim 2, characterized in that: In step (1), the pressure of oxygen in the reactor is 5.0 to 10.0 MPa.

6. The method for preparing 1,4:3,6-dianhydro-D-pyranose glucoside oxalate according to claim 2, characterized in that: In step (2), the extraction time is 1-5 min; the silica gel column chromatography uses petroleum ether and ethyl acetate as eluents, with a volume ratio of 3:1-1:1, and gradient elution.

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

8. The use according to claim 7, characterized in that: The 1,4:3,6-dianhydro-D-pyranose glucoside oxalate is used as a flavor in cigarettes, and the added amount is 5 to 100 ppm of the mass of the cigarette tobacco.

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

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