CN103159806B - The preparation method of vanillin food grade,1000.000000ine mesh glucoside and the application in tobacco flavoring thereof - Google Patents
The preparation method of vanillin food grade,1000.000000ine mesh glucoside and the application in tobacco flavoring thereof Download PDFInfo
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- CN103159806B CN103159806B CN201310061992.4A CN201310061992A CN103159806B CN 103159806 B CN103159806 B CN 103159806B CN 201310061992 A CN201310061992 A CN 201310061992A CN 103159806 B CN103159806 B CN 103159806B
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- 235000013305 food Nutrition 0.000 title claims abstract description 68
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 title claims abstract description 68
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 235000012141 vanillin Nutrition 0.000 title claims abstract description 68
- 229930182478 glucoside Natural products 0.000 title claims abstract description 59
- 150000008131 glucosides Chemical class 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 241000208125 Nicotiana Species 0.000 title abstract description 20
- 235000002637 Nicotiana tabacum Nutrition 0.000 title abstract description 20
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 14
- LPRNQMUKVDHCFX-UHFFFAOYSA-N Vanilloside Natural products COC1=CC(C=O)=CC=C1OC1C(O)C(O)C(O)C(CO)O1 LPRNQMUKVDHCFX-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 acetyl glucovanillin Chemical compound 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- LPRNQMUKVDHCFX-RGDJUOJXSA-N glucovanillin Natural products COC1=CC(C=O)=CC=C1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 LPRNQMUKVDHCFX-RGDJUOJXSA-N 0.000 claims abstract description 10
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims abstract 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- 229960001701 chloroform Drugs 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000012074 organic phase Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 14
- 239000008346 aqueous phase Substances 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 238000001953 recrystallisation Methods 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 235000015320 potassium carbonate Nutrition 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 235000019504 cigarettes Nutrition 0.000 abstract description 19
- 239000000796 flavoring agent Substances 0.000 abstract description 10
- 235000019634 flavors Nutrition 0.000 abstract description 10
- 239000000779 smoke Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 235000019633 pungent taste Nutrition 0.000 abstract description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 239000003205 fragrance Substances 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000011285 coke tar Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 125000003147 glycosyl group Chemical group 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 230000001953 sensory effect Effects 0.000 description 2
- 230000000391 smoking effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005285 chemical preparation method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000012207 quantitative assay Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Abstract
The invention provides a kind of preparation method of vanillin food grade,1000.000000ine mesh glucoside, first use tetra-acetylated acetylbromoglycose and vanillin food grade,1000.000000ine mesh Reactive Synthesis four acetyl glucovanillin, then use four acetyl glucovanillins and sodium methylate to be obtained by reacting vanillin food grade,1000.000000ine mesh glucoside.Vanillin food grade,1000.000000ine mesh glucoside provided by the present invention has reaction conditions gentleness, safety, and step is simple, is easy to the advantages such as suitability for industrialized production; Be applied in tobacco can significantly improve cigarette flavor rich, reduce side-stream smoke pungency, the cost of production of cigarettes can not be increased simultaneously, therefore have a wide range of applications at tobacco industry.
Description
Technical field
The present invention relates to fragrance-enhancing tobacco technical field, specifically a kind of preparation method of vanillin food grade,1000.000000ine mesh glucoside and the application in tobacco flavoring thereof.
Background technology
Flavour ingredient in tobacco not only exists with free state, but also exists with glucosides combined.Free state flavour ingredient processing, storage and transport process in easily volatilize, thus cause cigarette product loss of aroma or every mouthful of flavor concentration uneven.After flavour ingredient and glucose are combined into glucosides, just not there is volatility or volatility is very low, but under the condition of heating or enzymolysis, glycosidic link fracture can discharge flavour ingredient, thus produces contribution to smoke perfume, has important effect to solving the problem of fragrance inequality before and after low-coke tar cigarette.1989, the people such as Kapfer have studied the flavour ingredient that in tobacco, glucosides combines, result shows: free glucosides part does not have the fairly obvious action effect improving cigarette smoke fragrance, but when after the material forming glucosides combination, there is the fragrance effects significantly improving cigarette smoke, these strong products that close can enter in smoke condensate with main flume, and the quantitative assay rate of transform of such material in flue gas is about 10%.Therefore synthesize glucoside compound and apply in cigarette, can enrich cigarette cigarette monomer perfume material, the exploitation for low-coke tar cigarette provides foundation and support.
Vanillin food grade,1000.000000ine mesh and derivative thereof are a kind of important fragrance matters in tobacco, important impact is had on tobacco aroma quality and feature, its content in natural baccy flue gas is extremely low, although the cracking of vanillin food grade,1000.000000ine mesh glucoside can produce vanillin food grade,1000.000000ine mesh, but there is no the relevant report of chemical synthesis and preparation method at present, therefore its application in tobacco is restricted.
Summary of the invention
Object of the present invention provides a kind of chemical synthesis process of vanillin food grade,1000.000000ine mesh glucoside and the application method in tobacco thereof just for the deficiencies in the prior art, the molecular structure of vanillin food grade,1000.000000ine mesh glucoside as shown in Figure 5.
The object of the invention is to be achieved through the following technical solutions: a kind of preparation method of vanillin food grade,1000.000000ine mesh glucoside; first use tetra-acetylated acetylbromoglycose and vanillin food grade,1000.000000ine mesh Reactive Synthesis four acetyl glucovanillin, then use four acetyl glucovanillins and sodium methylate to be obtained by reacting vanillin food grade,1000.000000ine mesh glucoside.Concrete synthetic method is as follows:
The synthesis of (1) four acetyl glucovanillin: add trichloromethane in tetra-acetylated acetylbromoglycose, is transferred in constant pressure funnel after dissolving; Take be equivalent to tetra-acetylated acetylbromoglycose massfraction be 15% ~ 25% vanillin food grade,1000.000000ine mesh add in solution of potassium carbonate, be transferred in another constant pressure funnel after making it dissolve completely; Adding in the four-hole boiling flask being furnished with reflux condensing tube, thermometer and constant pressure funnel and being equivalent to tetra-acetylated acetylbromoglycose ~ massfraction is the Tetrabutyl amonium bromide of 5% ~ 10%, add water and trichloromethane again, the quality of water is 5 ~ 10 times of Tetrabutyl amonium bromide, the volume ratio of water and trichloromethane is 1:0.5 ~ 2, is heated to 40 ~ 60 DEG C of stirrings and makes it dissolve; Stir the vanillin food grade,1000.000000ine mesh solution of tetra-acetylated acetylbromoglycose solution and the salt of wormwood dissolving simultaneously dripping trichloromethane dissolving, maintain the temperature between 40 ~ 60 DEG C in dropping process; Then heated and stirred reaction 3 ~ 8h; Be cooled to room temperature after having reacted, add trichloromethane and water, the quality of water is 0.5 ~ 3 times of tetra-acetylated acetylbromoglycose, and the volume ratio of trichloromethane and water is 1:1 ~ 2, is separated upper strata aqueous phase and lower floor's organic phase; Then wash lower floor's organic phase with water 1 ~ 3 time, merge aqueous phase, aqueous phase trichloromethane is stripped 1 ~ 3 time; Merge lower floor organic phase, wash with water at every turn and be about 7 to pH and keep stablizing constant, collect organic phase and add anhydrous sodium sulfate drying; Rotary evaporation obtains the thick product of four acetyl glucovanillins; Add the dehydrated alcohol recrystallization of the thick product of four acetyl glucovanillins 3 ~ 10 times of quality, obtain described four acetyl glucovanillins, weigh (yield is about 50%).Four acetyl glucovanillin synthetic routes as shown in Figure 6.
(2) synthesis of vanillin food grade,1000.000000ine mesh glucoside: add the anhydrous methanol being equivalent to four acetyl glucovanillins, 10 ~ 20 times of quality in the four acetyl glucovanillins that step (1) is obtained, stir and make it dissolve completely; Drip after dissolving and be equivalent to the methanol solution that four acetyl glucovanillin massfractions are the sodium methylate of 0.1% ~ 1%, keep 40 ~ 60 DEG C of stirring reaction 30 ~ 90min; Reacted under putting into-10 ~-30 DEG C of environment and carried out recrystallization, suction filtration obtains vanillin food grade,1000.000000ine mesh glucoside crude product; Add vanillin food grade,1000.000000ine mesh glucoside crude product 3 ~ 20 times of quality methanol solution recrystallizations, obtain described vanillin food grade,1000.000000ine mesh glucoside, weigh (yield is about 70%).The synthetic route of vanillin food grade,1000.000000ine mesh glucoside as shown in Figure 7.
In order to confirm the structure of the vanillin food grade,1000.000000ine mesh glucoside that technological line of the present invention synthesizes, by infrared spectra, proton nmr spectra and carbon-13 nmr spectra carry out Analysis and Identification to product, and result is as follows:
1, adopt U.S. Nicolet company's T hermoNicoletAvatar370 type infrared spectrometric analyzer to analyze to synthesized product, infrared spectrogram as shown in Figure 1,3401cm
-1strong absorption peak be sugar associate hydrogen bond ν
o-Hstretching vibration absorption peak; After in glucosides, many-OH bases of glycosyl part form hydrogen bond association ,-O-H key elongates, and moment of dipole increases, and therefore shows as strong and wide peak; 2917.9cm
-1for the ν of methyl in vanillin food grade,1000.000000ine mesh aglucon
c-Habsorption peak; 1686.4cm
-1the characteristic absorbance ν of stretching vibration of vanillin food grade,1000.000000ine mesh aldehyde radical C=O
c=O; 1045.90cm
-1it is the stronger absorption peak caused by glycosyl part C-O-C asymmetrical stretching vibration.
2, adopt U.S. Bruker company BrukerAvanceAMX-400 type nuclear magnetic resonance analyser, obtain product
1hNMR collection of illustrative plates (D-DMSO is solvent), as shown in Figure 2,
1hNMR spectrum is without obvious Interference Peaks, and the molecular structure of contrast vanillin food grade,1000.000000ine mesh glucoside carries out structural characterization.H is tentatively attributed to: 2.50ppm is the hydrogen of No. 3 positions on glucose ring; 3.18-3.28ppm is the hydrogen of 2, No. 4 positions on glucose ring; 3.65 is the hydrogen of No. 3 positions on glucose ring; 3.84ppm is the hydrogen of the methoxyl group of No. 12 positions; 5.10ppm is the hydrogen of No. 6 positions on glucose ring; 7.27ppm be the hydrogen of No. 8 position phenyl ring; 7.51ppm be the hydrogen of No. 11 position phenyl ring; 7.53 be the hydrogen of No. 9 position phenyl ring; 9.86 is hydrogen on aldehyde radical.
3, adopt U.S. Bruker company BrukerAvanceAMX-400 type nuclear magnetic resonance analyser, obtain product
13cNMR collection of illustrative plates (D-DMSO is solvent), as shown in Figure 3.
13cNMR spectrum is without obvious Interference Peaks, and the molecular structure of contrast vanillin food grade,1000.000000ine mesh glucoside carries out structural characterization.C is tentatively attributed to: 39.82ppm is C13,55.95ppm be C6,60.87ppm is C5,73.38ppm is C4,77.12ppm be C3,77.46ppm is C2,99.66ppm is C1,110.74ppm be C11,114.82ppm is C8,125.72ppm is C9,120.81ppm is C10,125.72ppm be C9,149.51ppm is C12,152.05ppm is C7,191.89ppm is C14.
The analytical results of comprehensive infrared spectrogram, NMR (Nuclear Magnetic Resonance) spectrum figure, can determine that the structure of synthetic product and vanillin food grade,1000.000000ine mesh glucoside matches.
Vanillin food grade,1000.000000ine mesh glucoside synthesized by the present invention is applied in tobacco flavoring, it is characterized in that: vanillin food grade,1000.000000ine mesh glucoside is formed vanillin food grade,1000.000000ine mesh glucoside solution with the water dissolution of 1000 times, and vanillin food grade,1000.000000ine mesh glucoside solution and pipe tobacco add in pipe tobacco according to the mass ratio of 0.1 ~ 1.5:100
The different adding proportion of vanillin food grade,1000.000000ine mesh glucoside has different impacts to cigarette sensory evaluating smoking effect, present invention applicant carries out experimental study to vanillin food grade,1000.000000ine mesh glucoside different adding proportion in cigarette, by smokeing panel test, determine the suitable amounts scope of vanillin food grade,1000.000000ine mesh glucoside in cigarette and optimum amount.This experiment is by vanillin food grade,1000.000000ine mesh glucoside with the water dissolution of 1000 times, and be sprayed in pipe tobacco in the mode of perfuming by vanillin food grade,1000.000000ine mesh glucoside dissolution homogeneity, the mass ratio of vanillin food grade,1000.000000ine mesh glucoside solution and pipe tobacco is 0.1 ~ 2:100.Evaluation result is in table 1:
Table 1 vanillin food grade,1000.000000ine mesh glucoside applies ratio and cigarette sensory evaluation effect
Note: participate in totally ten six judging panels smoked panel test: wherein three is national judging panel, eight provincial judging panels, five level of factory judging panels.
According to smoking result, vanillin food grade,1000.000000ine mesh glucoside is rich to raising cigarette flavor, there is obvious effect reduction side-stream smoke pungency aspect, and after consumption to 2%, fragrance is oppressive to some extent, residual increasing.Therefore suitable amount 0.5 ~ 1.5% can be thought.Due to this experiment be first by vanillin food grade,1000.000000ine mesh glucoside with the water dissolution of 1000 times, the mass ratio made an addition to again in pipe tobacco is 0.1 ~ 2:100, as long as so add minute quantity vanillin food grade,1000.000000ine mesh glucoside to reach the effect significantly strengthening cigarette flavor, the cost using vanillin food grade,1000.000000ine mesh glucoside provided by the invention can not increase production of cigarettes is described.
Vanillin food grade,1000.000000ine mesh glucoside provided by the present invention has reaction conditions gentleness, safety, and step is simple, is easy to the advantages such as suitability for industrialized production; Be applied in tobacco can significantly improve cigarette flavor rich, reduce side-stream smoke pungency, the cost of production of cigarettes can not be increased simultaneously, therefore have a wide range of applications at tobacco industry.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the vanillin food grade,1000.000000ine mesh glucoside adopting the present invention's synthesis;
Fig. 2 is the vanillin food grade,1000.000000ine mesh glucoside adopting the present invention's synthesis
1hNMR schemes;
Fig. 3 is the 13CNMR figure of the vanillin food grade,1000.000000ine mesh glucoside adopting the present invention's synthesis;
Fig. 4 is the high resolution mass spectrum figure of the vanillin food grade,1000.000000ine mesh glucoside adopting embodiment of the present invention synthesis;
Fig. 5 is the molecular structure of vanillin food grade,1000.000000ine mesh glucoside;
Fig. 6 is the synthetic route chart of four acetyl glucovanillins;
Fig. 7 is the synthetic route chart of vanillin food grade,1000.000000ine mesh glucoside.
Embodiment
Below in conjunction with specific embodiment, the technical scheme in the present invention is clearly and completely described.
Embodiment 1:
The synthesis of step one, four acetyl glucovanillins
Add trichloromethane with triangular flask and dissolve the tetra-acetylated acetylbromoglycose of 100g, be transferred in constant pressure funnel after dissolving completely; Claim 20g vanillin food grade,1000.000000ine mesh to add in solution of potassium carbonate, be transferred in another constant pressure funnel after making it dissolve completely; In the four-hole boiling flask being furnished with reflux condensing tube, thermometer and constant pressure funnel, add 7g Tetrabutyl amonium bromide, then add 50ml water and 50ml trichloromethane, be heated to the 45 DEG C of stirrings of outer temperature and make it dissolve; Stir the vanillin food grade,1000.000000ine mesh solution of tetra-acetylated acetylbromoglycose solution and the salt of wormwood dissolving simultaneously dripping the dissolving of above-mentioned trichloromethane, in dropping process, keep outer temperature 45 DEG C; Then heated and stirred reaction 6h; Be cooled to room temperature after having reacted, add 70ml trichloromethane and 100ml water, be transferred to separating funnel, be separated upper strata aqueous phase, retain lower floor's organic phase; Then wash lower floor's organic phase 2 times with 50mL, merge aqueous phase, aqueous phase 40mL trichloromethane is stripped 2 times; Merge lower floor's organic phase, be washed to pH with 60mL constant at every turn, collect organic phase and add anhydrous sodium sulfate drying; Rotary evaporation obtains the thick product of four acetyl glucovanillins; Add 340ml dehydrated alcohol recrystallization, weigh (about having 52g).
The synthesis of step 2, vanillin food grade,1000.000000ine mesh glucoside
In there-necked flask, add 40g tetra-acetyl glucovanillin, then add 650ml anhydrous methanol, stir and make it dissolve completely; After dissolving, constant pressure funnel drips the methanol solution of 20ml containing 0.2g sodium methylate, temperature 40 DEG C of stirring reaction 60min in keeping; Reacted under putting into-20 DEG C of environment and carried out recrystallization, suction filtration obtains crude product; Crude product adds 540ml methanol solution recrystallization, weighs (being about 29g).
Embodiment 2:
The synthesis of step one, four acetyl glucovanillins
Add trichloromethane with triangular flask and dissolve the tetra-acetylated acetylbromoglycose of 50g, be transferred in constant pressure funnel after dissolving completely; Claim 10g vanillin food grade,1000.000000ine mesh to add in solution of potassium carbonate, be transferred in another constant pressure funnel after making it dissolve completely; Be furnished with reflux condensing tube, in the four-hole boiling flask of thermometer and constant pressure funnel, adding 4g Tetrabutyl amonium bromide, then adding 40ml water and 40ml trichloromethane, be heated to the 50 DEG C of stirrings of outer temperature and make it dissolve; Stir the vanillin food grade,1000.000000ine mesh solution of tetra-acetylated acetylbromoglycose solution and the salt of wormwood dissolving simultaneously dripping trichloromethane dissolving, in dropping process, keep outer temperature 50 DEG C; Then heated and stirred reaction 5h; Be cooled to room temperature after having reacted, add 50ml trichloromethane and 70ml water, be transferred to separating funnel, be separated upper strata aqueous phase, retain lower floor's organic phase; Then wash lower floor's organic phase 3 times with 40mL, merge aqueous phase, aqueous phase 40mL trichloromethane is stripped 3 times; Merge lower floor's organic phase, be washed to pH with 50mL constant at every turn, collect organic phase and add anhydrous sodium sulfate drying; Rotary evaporation obtains the thick product of four acetyl glucovanillins; Add 200ml dehydrated alcohol recrystallization, weigh (about having 27g).
The synthesis of step 2, vanillin food grade,1000.000000ine mesh glucoside
In there-necked flask, add 25g tetra-acetyl glucovanillin, then add 400ml anhydrous methanol, stir and make it dissolve completely; After dissolving, constant pressure funnel drips the methanol solution of 15ml containing 0.1g sodium methylate, temperature 45 DEG C of stirring reaction 70min in keeping; Reacted under putting into-18 DEG C of environment and carried out recrystallization, suction filtration obtains crude product; Crude product adds 400ml methanol solution recrystallization, weighs (being about 18g).
Respectively high resolution mass spectrum analysis is carried out to the product synthesized by above-described embodiment, the accurate molecular weight of vanillin food grade,1000.000000ine mesh glucoside: 314.1002, after vanillin food grade,1000.000000ine mesh glucoside combines with a sodium atom (22.989768) in high-resolution mass spectrometer, the accurate molecular weight of practical measurement is: 337.0896, result as shown in Figure 4, its accurate theoretical molecular is: 337.0897, this illustrate synthesized by the present embodiment target compound---the structure of vanillin food grade,1000.000000ine mesh glucoside is correct.
Claims (1)
1. the preparation method of a vanillin food grade,1000.000000ine mesh glucoside; it is characterized in that: first use tetra-acetylated acetylbromoglycose and vanillin food grade,1000.000000ine mesh Reactive Synthesis four acetyl glucovanillin; then use four acetyl glucovanillins and sodium methylate to be obtained by reacting vanillin food grade,1000.000000ine mesh glucoside, concrete synthesis step is:
The synthesis of (1) four acetyl glucovanillin: add trichloromethane in tetra-acetylated acetylbromoglycose, is transferred in constant pressure funnel after dissolving; Take be equivalent to tetra-acetylated acetylbromoglycose massfraction be 15% ~ 25% vanillin food grade,1000.000000ine mesh add in solution of potassium carbonate, be transferred in another constant pressure funnel after making it dissolve completely; Adding in the four-hole boiling flask being furnished with reflux condensing tube, thermometer and constant pressure funnel and being equivalent to tetra-acetylated acetylbromoglycose massfraction is the Tetrabutyl amonium bromide of 5% ~ 10%, add water and trichloromethane again, the quality of water is 5 ~ 10 times of Tetrabutyl amonium bromide, the volume ratio of water and trichloromethane is 1: 0.5 ~ 2, is heated to 40 ~ 60 DEG C of stirrings and makes it dissolve; Stir the vanillin food grade,1000.000000ine mesh solution of tetra-acetylated acetylbromoglycose solution and the salt of wormwood dissolving simultaneously dripping trichloromethane dissolving, maintain the temperature between 40 ~ 60 DEG C in dropping process; Then heated and stirred reaction 3 ~ 8h; Be cooled to room temperature after having reacted, add trichloromethane and water, the quality of water is 0.5 ~ 3 times of tetra-acetylated acetylbromoglycose, and the volume ratio of trichloromethane and water is 1: 1 ~ 2, is separated upper strata aqueous phase and lower floor's organic phase; Then wash lower floor's organic phase with water 1 ~ 3 time, merge aqueous phase, aqueous phase trichloromethane is stripped 1 ~ 3 time; Merge lower floor organic phase, wash with water at every turn and be 7 to pH and keep stablizing constant, collect organic phase and add anhydrous sodium sulfate drying; Rotary evaporation obtains the thick product of four acetyl glucovanillins; Add the dehydrated alcohol recrystallization of the thick product of four acetyl glucovanillins 3 ~ 10 times of quality, obtain described four acetyl glucovanillins;
(2) synthesis of vanillin food grade,1000.000000ine mesh glucoside: add the anhydrous methanol being equivalent to four acetyl glucovanillins, 10 ~ 20 times of quality in the four acetyl glucovanillins that step (1) is obtained, stir and make it dissolve completely; Drip after dissolving and be equivalent to the methanol solution that four acetyl glucovanillin massfractions are the sodium methylate of 0.1% ~ 1%, keep 40 ~ 60 DEG C of stirring reaction 30 ~ 90min; Reacted under putting into-10 ~-30 DEG C of environment and carried out recrystallization, suction filtration obtains vanillin food grade,1000.000000ine mesh glucoside crude product; Add vanillin food grade,1000.000000ine mesh glucoside crude product 3 ~ 20 times of quality methanol solution recrystallizations, obtain described vanillin food grade,1000.000000ine mesh glucoside.
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| CN106397498B (en) * | 2016-08-31 | 2019-03-19 | 重庆欣欣向荣精细化工有限公司 | A kind of production method of Ethyl vanillin glucoside |
| CN109628420B (en) * | 2018-12-29 | 2020-10-02 | 浙江工业大学 | Glucosyltransferase and application thereof in producing vanillin-alpha-D-glucoside |
| KR102267982B1 (en) * | 2020-07-09 | 2021-06-21 | 주식회사 케이티앤지 | Vanilla smoking material wrapper and smoking article containing same |
| CN113197296B (en) * | 2021-06-03 | 2023-06-16 | 云南中烟工业有限责任公司 | Method for reducing sweetness of glucose solution by using vanillin |
| CN113788868B (en) * | 2021-10-19 | 2023-02-10 | 云南中烟工业有限责任公司 | Glucoside compound, preparation method and application thereof |
| CN114947173B (en) * | 2022-06-24 | 2023-06-23 | 湖北中烟工业有限责任公司 | Electronic cigarette atomizing agent containing glucoside and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0620982A1 (en) * | 1993-04-06 | 1994-10-26 | British-American Tobacco Company Limited | Flavouring smoking articles with vanillin glycoside |
| CN101157711A (en) * | 2007-09-28 | 2008-04-09 | 西安交通大学 | Compound having antineoplastic activity and uses thereof |
| CN101671375A (en) * | 2009-09-23 | 2010-03-17 | 华宝食用香精香料（上海）有限公司 | Bromotetraacetylglucose, synthetic method and use thereof |
| CN102617659A (en) * | 2012-03-09 | 2012-08-01 | 中国烟草总公司郑州烟草研究院 | Synthesis method for alpha-ionol glucoside, and application of alpha-ionol glucoside to flavoring of cigarettes |
-
2013
- 2013-02-27 CN CN201310061992.4A patent/CN103159806B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0620982A1 (en) * | 1993-04-06 | 1994-10-26 | British-American Tobacco Company Limited | Flavouring smoking articles with vanillin glycoside |
| CN101157711A (en) * | 2007-09-28 | 2008-04-09 | 西安交通大学 | Compound having antineoplastic activity and uses thereof |
| CN101671375A (en) * | 2009-09-23 | 2010-03-17 | 华宝食用香精香料（上海）有限公司 | Bromotetraacetylglucose, synthetic method and use thereof |
| CN102617659A (en) * | 2012-03-09 | 2012-08-01 | 中国烟草总公司郑州烟草研究院 | Synthesis method for alpha-ionol glucoside, and application of alpha-ionol glucoside to flavoring of cigarettes |
Non-Patent Citations (3)
| Title |
|---|
| 烟用潜香物质的分子设计;缪明明，等;《烟草科技》;19971231(第6期);第26页 * |
| 葡萄糖苷的热解研究;章平毅，等;《香料香精化妆品》;20020630(第3期);第7页右栏第3段第1-5行 * |
| 葡萄糖香草醛的相转移催化合成法;李雯，等;《河南科学》;19990930;第17卷(第3期);第252页第5-11段 * |
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