CN104478953A - Method for preparing cigarette fragrance releaser with honey sweet note - Google Patents
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- CN104478953A CN104478953A CN201410637497.8A CN201410637497A CN104478953A CN 104478953 A CN104478953 A CN 104478953A CN 201410637497 A CN201410637497 A CN 201410637497A CN 104478953 A CN104478953 A CN 104478953A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/18—Acyclic radicals, substituted by carbocyclic rings
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/18—Treatment of tobacco products or tobacco substitutes
- A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
- A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
- A24B15/36—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring
- A24B15/40—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring having only oxygen or sulfur as hetero atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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Abstract
The invention discloses a method for preparing an effective ingredient of a cigarette fragrance releaser with honey sweet note. The method comprises the steps: using an improved Koenigs-Knorr reaction to prepare benzyl-beta-D-glucopyranoside, after glucose acetylation, carrying out a reaction with hydrogen bromide, and thus obtaining alpha-tetraacetyl glucose bromide; and after a reaction solution is washed, mixing with a certain proportion of benzyl alcohol and silver oxide, carrying out a light-shielding reaction, to obtain benzyl-tetraacetyl-beta-D-glucopyranoside, then carrying out a deacetylation reaction, separating and purifying by a silica gel chromatography column, and thus obtaining a benzyl-beta-D-glucopyranoside pure product. The prepared benzyl-beta-D-glucopyranoside is cracked at a temperature of 300 DEG C and can release the target fragrance ingredient benzyl alcohol with the honey sweet note in mainstream smoke and sidestream smoke. The prepared cigarette fragrance releaser with the honey sweet note has the advantages of simple and easy method, low material price, easily available materials, and simple reaction equipment.
Description
Technical field
Embodiments of the present invention relate to essence spice for cigarette synthesis and applied technical field, and more specifically, embodiments of the present invention relate to a kind of preparation method with the fragrance releasing agent for tobacco of sweet note.
Background technology
Phenylcarbinol is a kind of colourless liquid, has sweet fragrance, is usually used in daily essence formula.Due to phenylcarbinol monomer high volatility, lasting is not lasting in use, is difficult to continue to play sweet perfume effect.In order to improve the conventional essence spice for cigarette in use not lasting problem of lasting, flavor precursor is used to be a good terms of settlement.Glucosides, as a class flavor precursor, itself does not have fragrance and volatility, but utilizes the fracture of glycosidic link by thermal treatment (as cigarette burning), and cracking produces volatile fragrance matter.Glucosides is the naturally occurring material of a class, and be usually present in plant materials, content is lower, is difficult to separating-purifying, and general needs just can obtain the pure substance with specific aglycone by synthesis.
At present, both at home and abroad for the study on the synthesis of glucosides, wherein the most classical is utilize Koeni
gglucosides is prepared in s-Knorr reaction; this method reacts comparatively violent when the alpha-brominated tetra-acetylated glucose of synthetic mesophase product; affect reaction yield; need after reaction to utilize the purification techniques such as recrystallization to carry out purifying to alpha-brominated tetra-acetylated glucose crude product, the sterling obtained is obtained by reacting corresponding glucosides to alcohols material again under the katalysis of silver salt.Require higher to purification technique in reaction process, operation steps is more miscellaneous, and because separating-purifying step is many, the loss of intermediate product in purification process is can hardly be avoided, and conventional operator, if lacked experience, are difficult to obtain desirable productive rate.In addition on the one hand, the time needed due to recrystallization is longer, and the alpha-brominated tetra-acetylated glucose stability of midbody product is poor, and separating-purifying process time can cause product deterioration too for a long time, can affect reaction yield equally.Domestic also have the report utilizing commercial alpha-brominated tetra-acetylated glucose to carry out glycoside synthesis as raw material, but this produce market price costly, poor stability, higher by this method synthesis production cost.
Summary of the invention
Instant invention overcomes the deficiencies in the prior art, there is provided a kind of embodiment with the preparation method of the fragrance releasing agent for tobacco of sweet note, to expect that utilizing the Koenigs-Knorr reaction improved to prepare benzyl-β-D-glucopyranoside solves the problem that when prior art prepares benzyl-β-D-glucopyranoside, intermediate product loss is many and target product productive rate is low.
The sweet note fragrance releasing agent for tobacco benzyl-β-D-glucopyranoside of invention, its structure is as follows:
For solving above-mentioned technical problem, one embodiment of the present invention by the following technical solutions:
Have a preparation method for the fragrance releasing agent for tobacco of sweet note, it adopts following operation steps:
The preparation of A, alpha-brominated tetra-acetylated glucose crude product
Glucose is obtained acetyl glucose solution in diacetyl oxide after acetylize, in acetyl glucose solution, slowly add saturated hydrogen bromide solution again carry out reacting the reaction mixture obtained containing alpha-brominated tetra-acetylated glucose, reaction mixture easier layering when then ensuing icy salt solution being washed reaction mixture diluted ethyl acetate, use icy salt solution, saturated potassium hydrogen carbonate solution washing more successively, isolate organic phase, organic phase through anhydrous sodium sulfate drying, concentrated obtain alpha-brominated tetra-acetylated glucose crude product;
The preparation of B, reaction intermediate benzyl-tetra-acetylated-β-D-glucopyranoside
The alpha-brominated tetra-acetylated glucose crude product of steps A is mixed with appropriate phenylcarbinol and silver suboxide, add 4A molecular sieve as water-retaining agent, and be solvent with ethyl acetate, under room temperature, lucifuge reaction obtains reaction intermediate benzyl-tetra-acetylated-β-D-glucopyranoside in 24-48 hour;
The preparation of C, benzyl-β-D-glucopyranoside
The reaction intermediate of step B is filtered, filtrate removes solvent through concentrating under reduced pressure, then add triethylamine/methanol/water mixing solutions to it and obtain reaction solution, at room temperature react concentrating under reduced pressure after 12 hours and remove solvent, then adopt silica gel column chromatograph to purify reaction solution, obtain object product benzyl-β-D-glucopyranoside sterling.
Reaction process can be expressed as:
Further technical scheme is: described in steps A, glucose, diacetyl oxide and saturated hydrogen bromide solution are with mass ratio 1:(15 ~ 30): (1 ~ 3) reacts at 15 ~ 25 DEG C the reaction mixture obtained for 10 ~ 30 minutes containing alpha-brominated tetra-acetylated glucose.
Further technical scheme is: described in step B, the mass ratio of phenylcarbinol, silver suboxide and 4A molecular sieve is 1:(1 ~ 4): (1 ~ 3).
Further technical scheme is: the triethylamine of triethylamine described in step C/methanol/water mixing solutions, the volume ratio of first alcohol and water are 1:(4 ~ 12): (1 ~ 3).
Preferably, the triethylamine of triethylamine described in step C/methanol/water mixing solutions, the volume ratio of first alcohol and water are 1:(10 ~ 12): 1.
Further technical scheme is: the elutriant adopting silica gel column chromatograph to carry out purifying described in step C is volume ratio is 1:(2 ~ 10) methyl alcohol/chloroform mixed solvent.
The catalyzer that acetylize described in steps A uses can adopt perchloric acid; glucose can be 3.6g:0.05mL with the ratio of the quality-volume of perchloric acid; but be not limited only to this, perchloric acid belongs to conventional catalyst, its consumption can adjust according to the needs of catalytic effect.
Benzyl-β-D-glucopyranoside prepared by the present invention is the precursor of sweet note fragrance releasing agent for tobacco, about 300 DEG C cracking, effectively can discharge and have sweet note flavour ingredient phenylcarbinol, and can show sweet note in main flow and flow measurement flue gas.Phenylcarbinol is a kind of colourless liquid, has sweet fragrance, is usually used in daily essence formula.Due to phenylcarbinol monomer high volatility, lasting is not lasting in use, is difficult to the effect playing sweet perfume (or spice).Sweet note fragrance releasing agent for tobacco and phenylcarbinol monomer are configured to the solution of same concentrations, add on blank cigarette respectively, smoking machine is utilized to trap flue gas, carry out gaschromatographic mass spectrometric analysis, the content that result shows phenylcarbinol in the former flue gas composition is 3.6 times of the latter, thus demonstrates sweet note fragrance releasing agent for tobacco prepared by the present invention and effectively can discharge target flavour ingredient phenylcarbinol.
Compared with prior art, one of beneficial effect of the present invention is: (1) raw material used in the present invention is simple and easy to get.The method of domestic report, the alpha-brominated tetra-acetylated glucose bought that adopts as raw material more, and alpha-brominated tetra-acetylated glucose is expensive, and unstable.The present invention adopts glucose to be the alpha-brominated tetra-acetylated glucose of Material synthesis, and material is dirt cheap, and saves production cost.(2) reactions steps of the present invention is simple, be that raw material only needs three steps just can obtain target product, and productive rate is higher with glucose.The method of domestic and international report, adopt red phosphorus, bromine and water and acetyl glucose to react when synthesizing alpha-brominated tetra-acetylated glucose, react comparatively violent, affect reaction yield, need to utilize column chromatography technology or recrystallization technology to carry out separating-purifying after reaction and obtain crystalloid sterling; The present invention directly adopts saturated hydrogen bromide solution to carry out the alpha-brominated tetra-acetylated glucose of Reactive Synthesis; reaction is comparatively gentle; productive rate is higher; reaction terminates rear employing simple washing methods and is removed by unreacted reactant; intermediate product does not need to carry out independent separating-purifying, decreases the loss of product in lengthy and jumbled separating-purifying step, and the productive rate of target product can reach 85%; treatment process is simple, and efficiency improves.(3) the sweet note fragrance releasing agent for tobacco of the present invention's synthesis is compared with traditional monomer flavour ingredient, and Heat stability is good is not volatile, and the amount of the sweet Studies of The Aromatic Substances phenylcarbinol that fragrance releasing agent discharges is comparatively large, and stable lasting.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of benzyl-β-D-glucopyranoside prepared by the present invention.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
The preparation of alpha-brominated tetra-acetylated glucose: 3.6g glucose is joined in the diacetyl oxide of 80g, under the catalysis of 0.05mL perchloric acid, acetylize obtains acetyl glucose solution, (add in 30 minutes to obtaining slowly adding the saturated hydrogen bromide solution of 8g in acetyl glucose solution, glucose, the mass ratio of diacetyl oxide and bag and hydrogen bromide solution is 1:22.2:2.2), hydrogen bromide and acetyl glucose react, generate alpha-brominated tetra-acetylated glucose, reaction mixture 40mL diluted ethyl acetate, use 50mL icy salt solution successively, 50mL saturated potassium hydrogen carbonate solution washing, isolate organic phase, dry, concentrated, obtain alpha-brominated tetra-acetylated glucose crude product, the alpha-brominated tetra-acetylated glucose of product is obtained with Diethyl ether recrystallization, productive rate is 96%.
Embodiment 2
The preparation of alpha-brominated tetra-acetylated glucose: 3.6g glucose is joined in the diacetyl oxide of 60g, under the catalysis of 0.05mL perchloric acid, acetylize obtains acetyl glucose solution, (add in 30 minutes to obtaining slowly adding the saturated hydrogen bromide solution of 10.5g in acetyl glucose solution, glucose, the mass ratio of diacetyl oxide and saturated hydrogen bromide solution is 1:16.7:2.9), at 15 DEG C, hydrogen bromide and acetyl glucose react 30 minutes, generate alpha-brominated tetra-acetylated glucose, after reaction terminates, with 40mL diluted ethyl acetate reaction mixture, use 50mL icy salt solution successively, 50mL saturated potassium hydrogen carbonate solution washing, isolate organic phase, then by organic phase through anhydrous sodium sulfate drying, concentrated, obtain alpha-brominated tetra-acetylated glucose crude product, the alpha-brominated tetra-acetylated glucose of product is obtained with Diethyl ether recrystallization, productive rate is 90%.
The comparative example of embodiment 1 and 2
React according to the Koenigs-Knorr of classics, 10g glucose is joined in the solution of acetic anhydride of 40g in batches, make the temperature of reaction mixture maintain 20-30 DEG C, acetylize under the catalysis of 0.24mL perchloric acid.Be cooled to room temperature, add 3.1g red phosphorus, then dropwise add the bromine of 5.8mL.Cooling, add the water of 3.6g under stirring, control temperature is no more than 20 DEG C; Reaction mixture sat 2 hours, uses 30mL dchloromethane, filters.80mL frozen water washs 2 times, then washs with the saturated sodium bicarbonate solution that 50mL is cold, anhydrous sodium sulfate drying, filters, concentrated, adds ether, obtains crude product.Obtain alpha-brominated tetra-acetylated glucose with Diethyl ether recrystallization, productive rate is 81%, all lower than the productive rate of embodiment 1 and embodiment 2.
Embodiment 3
The preparation of reaction intermediate benzyl-tetra-acetylated-β-D-glucopyranoside: 3.6g glucose is joined in the diacetyl oxide of 80g, under the catalysis of 0.05mL perchloric acid, acetylize obtains acetyl glucose solution, the saturated hydrogen bromide solution of 5.8g (adding in 30 minutes) is slowly added in acetyl glucose solution, at 25 DEG C, hydrogen bromide and acetyl glucose react 10 minutes, generate alpha-brominated tetra-acetylated glucose, after reaction terminates, with 40mL diluted ethyl acetate reaction mixture, use 50mL icy salt solution successively, 50mL saturated potassium hydrogen carbonate solution washing, isolate organic phase, then by organic phase through anhydrous sodium sulfate drying, concentrated, obtain alpha-brominated tetra-acetylated glucose crude product, by itself and 2.2g phenylcarbinol, 2.3g silver suboxide, the 4A molecular sieve of 4g, 40mL ethyl acetate mixes, and under room temperature, lucifuge reacts 48 hours, reacted mixture filters, remove solvent through concentrating under reduced pressure, adopt silica gel column chromatograph to carry out purifying (leacheate ethyl acetate and sherwood oil, volume ratio 1:6), obtain benzyl-tetra-acetylated-β-D-glucopyranoside sterling, productive rate is 89%.
The comparative example of embodiment 3
React according to the Koenigs-Knorr of classics, 10g glucose is joined in the diacetyl oxide of 40g in batches, make the temperature of reaction mixture maintain 20-30 DEG C, acetylize under the catalysis of 0.24mL perchloric acid.Be cooled to room temperature, add 3.1g red phosphorus, then dropwise add the bromine of 5.8mL.Cooling, add the water of 3.6g under stirring, control temperature is no more than 20 DEG C; Reaction mixture sat 2 hours, uses 30mL dchloromethane, filters.80mL frozen water washs 2 times, then washs with the saturated sodium bicarbonate solution that 50mL is cold, anhydrous sodium sulfate drying, filters, concentrated, adds ether, obtains crude product.The alpha-brominated tetra-acetylated glucose of final product is obtained with Diethyl ether recrystallization.By 6.48g phenylcarbinol, 8.28g silver carbonate, 10g anhydrous calciumsulphate, 50mL methylene dichloride fully mixes.After the alpha-brominated tetra-acetylated glucose 50mL methylene dichloride of end product fully dissolves; add in said mixture; stir lower reaction after 24 hours; filter, underpressure distillation, except desolventizing, is undertaken purifying (leacheate ethyl acetate and sherwood oil by silica gel column chromatography; volume ratio 1:6); obtain benzyl-tetra-acetylated-β-D-glucopyranoside sterling, productive rate is 72%, obviously low than embodiment 3 by 17%.
Embodiment 4
The preparation of benzyl-β-D-glucopyranoside: 3.6g glucose is joined in the diacetyl oxide of 80g, acetylize under the catalysis of 0.05mL perchloric acid, the saturated hydrogen bromide solution of 5.8g (adding in 30 minutes) is slowly added in glucose solution, at 20 DEG C, hydrogen bromide and acetyl glucose react, generate alpha-brominated tetra-acetylated glucose, reaction mixture 40mL diluted ethyl acetate, use 50mL icy salt solution, 50mL saturated potassium hydrogen carbonate solution washing successively, isolate organic phase, dry, concentrated, obtain alpha-brominated tetra-acetylated glucose crude product; By itself and 2.2g phenylcarbinol, 2.3g silver suboxide, the 4A molecular sieve of 4g, 40mL ethyl acetate mixes, and lucifuge reacts 24 hours; Reacted mixture filters, solvent is removed through concentrating under reduced pressure, add triethylamine/methanol/water mixing solutions 50mL (volume ratio 1:5:2), react 12 hours under room temperature, concentrating under reduced pressure removes solvent, adopts silica gel column chromatograph to carry out purifying (leacheate methyl alcohol and chloroform, volume ratio 1:8), obtain benzyl-β-D-glucopyranoside sterling, productive rate is 74%.
The comparative example of embodiment 4
3.6g glucose is joined in the diacetyl oxide of 80g, acetylize under the catalysis of 0.05mL perchloric acid, the saturated hydrogen bromide solution of 5.8g (adding in 30 minutes) is slowly added in glucose solution, hydrogen bromide and acetyl glucose react, generate alpha-brominated tetra-acetylated glucose, reaction mixture 40mL diluted ethyl acetate, use 50mL icy salt solution, 50mL saturated potassium hydrogen carbonate solution washing successively, isolate organic phase, dry, concentrated, obtain alpha-brominated tetra-acetylated glucose crude product; By itself and 2.2g phenylcarbinol, 2.3g silver suboxide, the 4A molecular sieve of 4g, 40mL ethyl acetate mixes, and lucifuge reacts 24 hours; Reacted mixture filters, solvent is removed through concentrating under reduced pressure, add triethylamine/methanol/water mixing solutions 50mL (volume ratio 1:10:1), react 12 hours under room temperature, concentrating under reduced pressure removes solvent, silica gel column chromatograph is adopted to carry out purifying (leacheate methyl alcohol and chloroform, volume ratio 1:8), obtain benzyl-β-D-glucopyranoside sterling, productive rate is 85%, productivity ratio embodiment 4 is high by 11%, illustrates that the volume ratio of triethylamine/each composition of methanol/water mixing solutions produces larger impact to the productive rate of final benzyl-β-D-glucopyranoside sterling.
Embodiment 5
3.6g glucose is obtained acetyl glucose solution after acetylize in 108g diacetyl oxide under the catalysis of 0.05mL perchloric acid, in acetyl glucose solution, slowly add the saturated hydrogen bromide solution of 3.6g again carry out reacting (glucose, diacetyl oxide and saturated hydrogen bromide solution mass ratio are 1:30:1), temperature of reaction is 20 DEG C, reaction times is 20 minutes, obtain the reaction mixture containing alpha-brominated tetra-acetylated glucose, then reaction mixture is used 40mL diluted ethyl acetate, use 50mL icy salt solution successively again, 50mL saturated potassium hydrogen carbonate solution washing, isolate organic phase, organic phase is through anhydrous sodium sulfate drying, concentrate and obtain alpha-brominated tetra-acetylated glucose crude product, then alpha-brominated tetra-acetylated glucose crude product is mixed with 2.2g phenylcarbinol and 8.8g silver suboxide, add the 4A molecular sieve of 6.6g as water-retaining agent (phenylcarbinol, silver suboxide and 4A molecular sieve mass ratio are 1:4:3), and with 60mL ethyl acetate for solvent, under room temperature, lucifuge is reacted and is obtained reaction intermediate in 36 hours, reaction intermediate is filtered, filtrate removes solvent through concentrating under reduced pressure, then add triethylamine/methanol/water mixing solutions (the volume ratio 1:4:1 of triethylamine, first alcohol and water) to it and obtain reaction solution, at room temperature react concentrating under reduced pressure after 12 hours and remove solvent, then adopted by reaction solution silica gel column chromatograph (leacheate methyl alcohol/chloroform mixed solvent, volume ratio 1:2) to purify, obtain object product benzyl-β-D-glucopyranoside sterling,, productive rate is 80%.
Embodiment 6
3.6g glucose is obtained acetyl glucose solution after acetylize in 72g diacetyl oxide under the catalysis of 0.05mL perchloric acid, in acetyl glucose solution, slowly add the saturated hydrogen bromide solution of 10.8g again carry out reacting (glucose, diacetyl oxide and saturated hydrogen bromide solution mass ratio are 1:20:3), temperature of reaction is 20 DEG C, reaction times is 20 minutes, obtain the reaction mixture containing alpha-brominated tetra-acetylated glucose, then reaction mixture is used 40mL diluted ethyl acetate, use 50mL icy salt solution successively again, 50mL saturated potassium hydrogen carbonate solution washing, isolate organic phase, organic phase is through anhydrous sodium sulfate drying, concentrate and obtain alpha-brominated tetra-acetylated glucose crude product, then alpha-brominated tetra-acetylated glucose crude product is mixed with 2.2g phenylcarbinol and 2.2g silver suboxide, add the 4A molecular sieve of 2.2g as water-retaining agent (phenylcarbinol, silver suboxide and 4A molecular sieve mass ratio are 1:1:1), and with 40mL ethyl acetate for solvent, under room temperature, lucifuge is reacted and is obtained reaction intermediate in 40 hours, reaction intermediate is filtered, filtrate removes solvent through concentrating under reduced pressure, then add triethylamine/methanol/water mixing solutions (the volume ratio 1:12:2 of triethylamine, first alcohol and water) to it and obtain reaction solution, at room temperature react concentrating under reduced pressure after 12 hours and remove solvent, then reaction solution is adopted silica gel column chromatograph (leacheate methyl alcohol/chloroform mixed solvent, volume ratio 1:10) purify, obtain object product benzyl-β-D-glucopyranoside sterling, productive rate is 85%.
Product is carried out
1hNMR characterizes, and Fig. 1 is its hydrogen nuclear magnetic resonance spectrogram.The position of each hydrogen marks as follows: 3.22-3.34 (5H, H-2,3,4,5, and 1 H on 6); 3.62-3.66 (other 1 H on 1H, H-6); 3.82-3.86 (1H, C6-OH); 4.42-4.45 (1H, C2-OH); 4.66 (4H, C3,4-OH and H-1 '); 7.38 (5H, the H on monosubstituted phenyl ring)
According to the above results, product prepared by the present invention is benzyl-β-D-glucopyranoside.This glucosides can generate about 300 DEG C decomposition has sweet note flavour ingredient phenylcarbinol.Benzyl-β-D-glucopyranoside and phenylcarbinol are configured to the solution of same concentrations, be expelled in blank cigarette, captured gas composition on smoking machine, carry out gaschromatographic mass spectrometric analysis, result shows 3.6 times that the benzyl alcohol content collected in the former flue gas is the latter, demonstrates benzyl-β-D-glucopyranoside prepared by the present invention and effectively retains and discharge target flavour ingredient.
Although with reference to multiple explanatory embodiment of the present invention, invention has been described here, but, should be appreciated that, those skilled in the art can design a lot of other amendment and embodiment, these amendments and embodiment will drop within spirit disclosed in the present application and spirit.More particularly, in the scope of, accompanying drawing open in the application and claim, multiple modification and improvement can be carried out to the building block of subject combination layout and/or layout.Except the modification of carrying out building block and/or layout is with except improvement, to those skilled in the art, other purposes also will be obvious.
Claims (6)
1. there is a preparation method for the fragrance releasing agent for tobacco of sweet note, it is characterized in that it adopts following operation steps:
The preparation of A, alpha-brominated tetra-acetylated glucose crude product
Glucose is obtained acetyl glucose solution in diacetyl oxide after acetylize, in acetyl glucose solution, slowly add saturated hydrogen bromide solution again carry out reacting the reaction mixture obtained containing alpha-brominated tetra-acetylated glucose, then by reaction mixture diluted ethyl acetate, use icy salt solution, saturated potassium hydrogen carbonate solution washing more successively, isolate organic phase, organic phase through anhydrous sodium sulfate drying, concentrated obtain alpha-brominated tetra-acetylated glucose crude product;
The preparation of B, reaction intermediate benzyl-tetra-acetylated-β-D-glucopyranoside
The alpha-brominated tetra-acetylated glucose crude product of steps A is mixed with appropriate phenylcarbinol and silver suboxide, add 4A molecular sieve as water-retaining agent, and be solvent with ethyl acetate, under room temperature, lucifuge reaction to obtain reaction intermediate benzyl-tetra-acetylated-β-D-glucopyranoside for 24-48 hour; The preparation of C, benzyl-β-D-glucopyranoside
The reaction intermediate of step B is filtered, filtrate removes solvent through concentrating under reduced pressure, then add triethylamine/methanol/water mixing solutions to it and obtain reaction solution, at room temperature react concentrating under reduced pressure after 12 hours and remove solvent, then adopt silica gel column chromatograph to purify reaction solution, obtain object product benzyl-β-D-glucopyranoside sterling.
2. the preparation method with the fragrance releasing agent of sweet note according to claim 1, is characterized in that glucose described in steps A, diacetyl oxide and saturated hydrogen bromide solution are with mass ratio 1:(15 ~ 30): (1 ~ 3) reacts at 15 ~ 25 DEG C the reaction mixture obtained for 10 ~ 30 minutes containing alpha-brominated tetra-acetylated glucose.
3. the preparation method with the fragrance releasing agent of sweet note according to claim 1, is characterized in that the mass ratio of phenylcarbinol described in step B, silver suboxide and 4A molecular sieve is 1:(1 ~ 4): (1 ~ 3).
4. the preparation method with the fragrance releasing agent of sweet note according to claim 1, is characterized in that the triethylamine of triethylamine described in step C/methanol/water mixing solutions, the volume ratio of first alcohol and water is 1:(4 ~ 12): (1 ~ 3).
5. the preparation method with the fragrance releasing agent of sweet note according to claim 4, is characterized in that the triethylamine of triethylamine described in step C/methanol/water mixing solutions, the volume ratio of first alcohol and water is 1:(10 ~ 12): 1.
6. the preparation method with the fragrance releasing agent of sweet note according to claim 1, is characterized in that the elutriant adopting silica gel column chromatograph to carry out purifying described in step C be volume ratio is 1:(2 ~ 10) methyl alcohol/chloroform mixed solvent.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08245675A (en) * | 1995-03-13 | 1996-09-24 | Shin Etsu Chem Co Ltd | Production of cellotriose and cellotetraose monomer and oligomer therefrom |
| CN101130560A (en) * | 2007-08-10 | 2008-02-27 | 安徽农业大学 | Method for preparing rose cut flower flavouring agent and use method of flavouring agent |
| CN101607974A (en) * | 2009-07-16 | 2009-12-23 | 天津大学 | A kind of glucose probe and preparation method thereof with utilize carbohydrate chip of this glucose probe and preparation method thereof |
| CN101875675A (en) * | 2010-06-11 | 2010-11-03 | 江苏惠利隆塑业集团有限公司 | Preparation method of some glucoside |
| US20130252909A1 (en) * | 2012-03-23 | 2013-09-26 | University Of Iowa Research Foundation | Tannin inhibitors of hiv |
-
2014
- 2014-11-12 CN CN201410637497.8A patent/CN104478953A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08245675A (en) * | 1995-03-13 | 1996-09-24 | Shin Etsu Chem Co Ltd | Production of cellotriose and cellotetraose monomer and oligomer therefrom |
| CN101130560A (en) * | 2007-08-10 | 2008-02-27 | 安徽农业大学 | Method for preparing rose cut flower flavouring agent and use method of flavouring agent |
| CN101607974A (en) * | 2009-07-16 | 2009-12-23 | 天津大学 | A kind of glucose probe and preparation method thereof with utilize carbohydrate chip of this glucose probe and preparation method thereof |
| CN101875675A (en) * | 2010-06-11 | 2010-11-03 | 江苏惠利隆塑业集团有限公司 | Preparation method of some glucoside |
| US20130252909A1 (en) * | 2012-03-23 | 2013-09-26 | University Of Iowa Research Foundation | Tannin inhibitors of hiv |
Non-Patent Citations (3)
| Title |
|---|
| ASISH K SEN ET AL.: "Synthesis of 4-O- and 6-O-β-D-xylopyranosyl-D-glucopyranoses and their protein conjugates", 《INDIAN JOURNAL OF CHEMISTRY》 * |
| MO HUNSEN ET AL.: "Mild one-pot preparation of glycosyl bromides", 《CARBOHYDRATE RESEARCH》 * |
| RAYMOND, ALBETR L. ET AL.: "The substitution of glucose in position 4. II. 2,3-Diacetyl-β-benzylglucoside and its derivatives", 《JOURNAL OF BIOLOGICAL CHEMISTRY》 * |
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