CN117924378A - Preparation method and application of 1,4:3, 6-dianhydro-D-glucopyranose - Google Patents
Preparation method and application of 1,4:3, 6-dianhydro-D-glucopyranose Download PDFInfo
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- CN117924378A CN117924378A CN202410031353.1A CN202410031353A CN117924378A CN 117924378 A CN117924378 A CN 117924378A CN 202410031353 A CN202410031353 A CN 202410031353A CN 117924378 A CN117924378 A CN 117924378A
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- 238000000967 suction filtration Methods 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
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- GRGCWBWNLSTIEN-UHFFFAOYSA-N trifluoromethanesulfonyl chloride Chemical compound FC(F)(F)S(Cl)(=O)=O GRGCWBWNLSTIEN-UHFFFAOYSA-N 0.000 claims description 3
- JXRGUPLJCCDGKG-UHFFFAOYSA-N 4-nitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC=C(S(Cl)(=O)=O)C=C1 JXRGUPLJCCDGKG-UHFFFAOYSA-N 0.000 claims description 2
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- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 claims description 2
- OSHOQERNFGVVRH-UHFFFAOYSA-K iron(3+);trifluoromethanesulfonate Chemical compound [Fe+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F OSHOQERNFGVVRH-UHFFFAOYSA-K 0.000 claims description 2
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 claims 1
- HOVAGTYPODGVJG-ZFYZTMLRSA-N methyl alpha-D-glucopyranoside Chemical compound CO[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O HOVAGTYPODGVJG-ZFYZTMLRSA-N 0.000 claims 1
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- Saccharide Compounds (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method and application of 1,4:3, 6-dianhydro-D-glucopyranose. Compared with the synthesis method reported in the prior literature, the method has the advantages of low cost and easy obtainment of raw materials, simple reaction process, high total yield of three-step reaction of more than 65%, capability of large-scale production and wide application prospect. The fragrant raw material can be added into cigarettes to increase the sweet feeling of the oral cavity, enrich the fragrance of the cigarettes, increase the permeability and fineness of the smoke, improve the comfort of the aftertaste and have potential application value.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of 1,4:3, 6-dianhydro-D-glucopyranose and application of the 1,4:3, 6-dianhydro-D-glucopyranose serving as a sweet raw material in cigarettes.
Background
1,4:3, 6-Dianhydro-D-glucopyranose is commonly existing in cigarette smoke and saccharide cracking products, belongs to pyran compounds generated by saccharide degradation, and has the characteristics of volatility, fat solubility, water solubility and the like. However, few studies have been reported so far on the synthesis of this compound, and the synthesis process has been reported to be immature, and the cost of the product is high. In 1987, batelaan and the like, isomannide nitrate (price >5 ten thousand/g) or isosorbide nitrate (price >0.5 ten thousand/g) is used for pyrolysis under high temperature and high vacuum, and the synthetic method has the advantages of high price of raw materials, extremely severe reaction conditions, difficult control and difficult wide application. In 2007 Fabbri, the cellulose is directly thermally cracked at 350 ℃ without adding a catalyst, so that 3% of 1,4:3, 6-dianhydro-D-glucopyranose products can be obtained. In 2016, casoni and the like, when microcrystalline cellulose is used as a substrate and MCM-41 and Cu1-MCM-41 are used as catalysts for preparing biomass oil, the highest yield of 1,4:3, 6-dianhydro-D-glucopyranose components is about 6%, but the preparation process of the catalysts is complicated, and the yield is obviously reduced when the catalysts are repeatedly used.
The preparation method of the currently marketed 1,4:3, 6-dianhydro-D-glucopyranose standard substance is to collect cellulose combustion flue gas and purify the cellulose combustion flue gas by adopting a column chromatography method, so that the preparation cost is extremely high. Therefore, the development of a new method for synthesizing and researching the 1,4:3, 6-dianhydro-D-glucopyranose has important significance.
Disclosure of Invention
The invention aims to provide a preparation method of 1,4:3, 6-dianhydro-D-glucopyranose, which is simple to operate, high in yield and easy to produce in a large scale, and application of the preparation method serving as a sweet raw material for special cigarettes in cigarettes.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of 1,4:3, 6-dianhydro-D-glucopyranose comprises the following steps:
Step 1, preparing an intermediate compound (II): sequentially adding raw materials of methyl-alpha-D-glucopyranoside (I), a sulfonylation reagent, alkali and a solvent into a reaction bottle, stirring and reacting for 1-5 hours at the temperature of 0-10 ℃, adding a saturated sodium bicarbonate solution and a saturated sodium chloride solution for washing after the reaction is finished, extracting and separating to obtain an organic phase, drying the organic phase by using anhydrous Na 2SO4, and evaporating the solvent under reduced pressure to obtain an intermediate compound (II);
Step 2, intermediate compound (III) preparation: sequentially adding an intermediate compound (II), alkali and a solvent into a reaction bottle for reaction for 4-8 hours at the temperature of 40-80 ℃, and carrying out suction filtration after the reaction is finished, and concentrating filtrate under reduced pressure to obtain an intermediate compound (III);
Step 3, preparing a target product (IV): sequentially adding an intermediate compound (III), a catalyst and a solvent into a reaction bottle, reacting for 2-8 hours at 20-80 ℃, decompressing and evaporating the solvent after the reaction is finished, and separating a crude product by silica gel column chromatography to obtain a target product 1,4:3, 6-dianhydro-D-glucopyranose (IV).
Preferably, in the step 1, the sulfonylating agent is one of methanesulfonyl chloride, trifluoromethanesulfonyl chloride, benzenesulfonyl chloride, p-toluenesulfonyl chloride or p-nitrobenzenesulfonyl chloride; the alkali is one of potassium carbonate, triethylamine or pyridine; the solvent is one of acetonitrile, dichloromethane or tetrahydrofuran.
Preferably, in the step 1, the molar ratio of the methyl-alpha-D-glucopyranoside (I) to the sulfonylating agent is 1:1 (1.0-1.5).
Preferably, in step 2, the base is one of sodium hydride, potassium hydroxide or sodium hydroxide, and the solvent is one of acetonitrile, dichloromethane or tetrahydrofuran.
Preferably, in the step 2, the molar ratio of the intermediate compound (II) to the alkali is 1:1-5.
Preferably, in the step 3, the catalyst is one of p-toluenesulfonic acid, ferric triflate, ferric trichloride or ferric tribromide; the solvent is one of acetonitrile, methanol or tetrahydrofuran.
Preferably, in the step 3, the molar ratio of the intermediate compound (III) to the catalyst is 1: (0.1-3).
An application of the 1,4:3, 6-dianhydro-D-glucopyranose prepared by any one of the above materials as a sweet flavor raw material for cigarettes, which is applied to cigarettes.
Preferably, the addition amount of the 1,4:3, 6-dianhydro-D-glucopyranose serving as the sweet flavor raw material for cigarettes is 0.5-100 ppm of the mass of the tobacco shreds.
The beneficial effects of the invention are as follows:
according to the technical scheme, methyl-alpha-D-glucopyranoside is taken as an initial raw material, and 1,4:3, 6-dianhydro-D-glucopyranose is synthesized through three steps of reactions. Compared with the synthesis method reported in the prior literature, the method has the advantages of low cost and easy obtainment of raw materials, simple reaction process, high total yield of three-step reaction of more than 65%, capability of large-scale production and wide application prospect. The fragrant raw material can be added into cigarettes to increase the sweet feeling of the oral cavity, enrich the fragrance of the cigarettes, increase the permeability and fineness of the smoke, improve the comfort of the aftertaste and have potential application value.
Detailed Description
The following examples are given by way of illustration only and are not to be construed as limiting the scope of the invention.
In the following examples of the present application, reagents or instruments and the like used, unless otherwise specified, are available through normal commercial routes.
In the technical scheme of the application, for the synthesis of 1,4:3, 6-dianhydro-D-glucopyranose, three steps of reactions are adopted, and the reaction structural formula is shown as follows:
Example 1
A preparation method of 1,4:3, 6-dianhydro-D-glucopyranose comprises the following steps:
Step 1, preparing an intermediate compound (II): in a 100mL round bottom flask, 1.94g (10 mmol) of methyl-. Alpha. -D-glucopyranoside, 1.85g (11 mmol) of trifluoromethanesulfonyl chloride, 11.1 (11 mmol) of triethylamine and 20mL of acetonitrile were added, followed by reaction at 0℃for 2 hours. After the completion of the reaction, 20mL of a saturated sodium hydrogencarbonate solution and 20mL of a saturated sodium chloride solution were added to wash, and the organic phase was separated by extraction and dried over anhydrous Na 2SO4, and the solvent was distilled off under reduced pressure to obtain 3.07g of intermediate compound (II) in 94.3% yield.
Step 2, intermediate compound (III) preparation: 1.63g (5 mmol) of intermediate compound (II), 0.48g (20 mmol) of sodium hydride and 20mL of acetonitrile are sequentially added into a reaction bottle to react for 6 hours at 80 ℃, suction filtration is carried out after the reaction is finished, and the filtrate is concentrated under reduced pressure to obtain 0.74g of intermediate compound (III) with the yield of 84.0%.
Step 3, preparing a target product (IV): in a reaction bottle, 0.35g (2 mmol) of intermediate compound (III), 0.33g (2 mmol) of ferric chloride and 20mL of tetrahydrofuran are sequentially added for reaction at 50 ℃ for 8 hours, the solvent is distilled off under reduced pressure after the reaction is finished, and the crude product is separated by silica gel column chromatography to obtain 0.24g of target product 1,4:3, 6-dianhydro-D-glucopyranose (IV) with the yield of 83.3 percent. The total yield of the three-step reaction is 65.8 percent.
Example 2
A preparation method of 1,4:3, 6-dianhydro-D-glucopyranose comprises the following steps:
Step 1, preparing an intermediate compound (II): in a 100mL round bottom flask, 1.94g (10 mmol) of methyl-. Alpha. -D-glucopyranoside, 2.09g (11 mmol) of p-toluenesulfonyl chloride, 11.1 (11 mmol) of triethylamine and 20mL of acetonitrile were added, followed by reaction at 0℃for 2 hours. After the completion of the reaction, 20mL of a saturated sodium hydrogencarbonate solution and 20mL of a saturated sodium chloride solution were added to wash, and the organic phase was separated by extraction and dried over anhydrous Na 2SO4, and the solvent was distilled off under reduced pressure to obtain 3.22g of intermediate compound (II) in 92.5% yield.
Step 2, intermediate compound (III) preparation: 1.74g (5 mmol) of intermediate compound (II), 0.36g (15 mmol) of sodium hydride and 20mL of acetonitrile are sequentially added into a reaction bottle to react for 8 hours at 80 ℃, suction filtration is carried out after the reaction is finished, and the filtrate is concentrated under reduced pressure to obtain 0.76g of intermediate compound (III) with the yield of 86.4%.
Step 3, preparing a target product (IV): in a reaction bottle, 0.35g (2 mmol) of intermediate compound (III), 0.49g (3 mmol) of ferric chloride and 20mL of tetrahydrofuran are sequentially added for reaction at 50 ℃ for 8 hours, the solvent is distilled off under reduced pressure after the reaction is finished, and the crude product is separated by silica gel column chromatography to obtain 0.25g of target product 1,4:3, 6-dianhydro-D-glucopyranose (IV) with the yield of 86.8 percent. The total yield of the three steps of reaction is 67.4%.
In the examples of the present application, the reaction steps are the same as those of example 1, except that the catalyst, solvent, alkali, etc. of each step are different, and the differences are only differences in the reaction yields, so that the present application is not described and illustrated in the excessive examples, but the technical scheme of the present application is not represented to be applicable to the technical scheme of example 1 or example 2, but examples 1 and 2 are merely examples.
Fragrance performance test: weighing a certain amount of 1,4:3, 6-dianhydro-D-glucopyranose (IV), and diluting the mixture into 5% solution by using ethanol for later use. Weighing 100g of blank cigarette tobacco shreds without flavoring, uniformly spreading in a clean tray, uniformly spraying an ethanol solution of the compound IV on the tobacco shreds to obtain flavored tobacco shreds with specific gravity of 0.5ppm, 1ppm, 10ppm, 50ppm and 100ppm, sealing and standing for 4 hours, drying in a 50 ℃ oven, humidifying with distilled water to standard moisture (12%), rolling into standard cigarettes, balancing moisture (humidity 60% +/-2%, temperature 22+/-1 ℃) for 48 hours, and then evaluating. The control sample is a blank cigarette and is balanced for 48 hours under the same temperature and humidity conditions.
Table 1 sensory evaluation results
As can be seen from table 1: the 1,4:3, 6-dianhydro-D-glucopyranose has the functions of obviously improving and modifying the aroma of cigarettes, reducing the irritation, improving the taste and keeping the aftertaste clean and comfortable. The cigarette has outstanding sweet taste, obviously improves the sweet return characteristic of the cigarette smoke, and has obvious sweet and moist taste characteristics of the cigarette, and the recommended dosage is as follows: 0.5-100ppm.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (9)
1. A preparation method of 1,4:3, 6-dianhydro-D-glucopyranose is characterized by comprising the following steps:
Step 1, preparing an intermediate compound (II): sequentially adding raw materials of methyl-alpha-D-glucopyranoside (I), a sulfonylation reagent, alkali and a solvent into a reaction bottle, stirring and reacting for 1-5 hours at the temperature of 0-10 ℃, adding a saturated sodium bicarbonate solution and a saturated sodium chloride solution for washing after the reaction is finished, extracting and separating to obtain an organic phase, drying the organic phase by using anhydrous Na 2SO4, and evaporating the solvent under reduced pressure to obtain an intermediate compound (II);
Step 2, intermediate compound (III) preparation: sequentially adding an intermediate compound (II), alkali and a solvent into a reaction bottle for reaction for 4-8 hours at the temperature of 40-80 ℃, and carrying out suction filtration after the reaction is finished, and concentrating filtrate under reduced pressure to obtain an intermediate compound (III);
Step 3, preparing a target product (IV): sequentially adding an intermediate compound (III), a catalyst and a solvent into a reaction bottle, reacting for 2-8 hours at 20-80 ℃, decompressing and evaporating the solvent after the reaction is finished, and separating a crude product by silica gel column chromatography to obtain a target product 1,4:3, 6-dianhydro-D-glucopyranose (IV).
2. The method for preparing 1,4:3, 6-dianhydro-D-glucopyranose according to claim 1, wherein in the step 1, the sulfonylating agent is one of methanesulfonyl chloride, trifluoromethanesulfonyl chloride, benzenesulfonyl chloride, p-toluenesulfonyl chloride or p-nitrobenzenesulfonyl chloride; the alkali is one of potassium carbonate, triethylamine or pyridine; the solvent is one of acetonitrile, dichloromethane or tetrahydrofuran.
3. The method for producing 1,4:3, 6-dianhydro-D-glucopyranose according to claim 1, wherein the molar ratio of the methyl- α -D-glucopyranoside (I) to the sulfonylating agent in the step 1 is 1:1 (1.0 to 1.5).
4. The method for preparing 1,4:3, 6-dianhydro-D-glucopyranose according to claim 1, wherein in the step 2, the alkali is one of sodium hydride, potassium hydroxide or sodium hydroxide, and the solvent is one of acetonitrile, dichloromethane or tetrahydrofuran.
5. The process for producing 1,4:3, 6-dianhydro-D-glucopyranose according to claim 1, wherein in the step 2, the molar ratio of the intermediate compound (II) to the base is 1:1 to 5.
6. The method for preparing 1,4:3, 6-dianhydro-D-glucopyranose according to claim 1, wherein in the step 3, the catalyst is one of p-toluenesulfonic acid, ferric triflate, ferric trichloride or ferric tribromide; the solvent is one of acetonitrile, methanol or tetrahydrofuran.
7. The process for producing 1,4:3, 6-dianhydro-D-glucopyranose, according to claim 1, wherein in step 3, the molar ratio of the intermediate compound (III) to the catalyst is 1: (0.1 to 3).
8. Use of 1,4:3, 6-dianhydro-D-glucopyranose, prepared according to any of the preceding claims 1 to 7, as a raw material for a sweet taste for cigarettes, in cigarettes.
9. The use according to claim 8, characterized in that 1,4:3, 6-dianhydro-D-glucopyranose is added as a raw material for tobacco sweet flavor in an amount of 0.5-100 ppm based on the mass of tobacco shreds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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