CN103740782A - Preparation method of C5 fatty acid monosaccharide ester, application of C5 fatty acid monosaccharide ester in cigarettes and cigarette - Google Patents
Preparation method of C5 fatty acid monosaccharide ester, application of C5 fatty acid monosaccharide ester in cigarettes and cigarette Download PDFInfo
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- CN103740782A CN103740782A CN201410018531.3A CN201410018531A CN103740782A CN 103740782 A CN103740782 A CN 103740782A CN 201410018531 A CN201410018531 A CN 201410018531A CN 103740782 A CN103740782 A CN 103740782A
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Abstract
The invention discloses a preparation method of C5 fatty acid monosaccharide ester, an application of the C5 fatty acid monosaccharide ester in cigarettes and a cigarette. The preparation method comprises the following steps: (1) preparing a mixed ionic liquid, wherein the volume ratio of a hydrophilic ionic liquid to a hydrophobic ionic liquid in the mixed ionic liquid is 1:0.1-1:10; (2) adding a monosaccharide water solution with the volume 0.1-10 times that of the mixed ionic liquid into the mixed ionic liquid, uniformly mixing, carrying out reduced pressure concentration and water removal at the temperature of 50-60 DEG C, and removing the undissolved monosaccharide to obtain a supersaturated monosaccharide ionic liquid; (3) adding C5 fatty acid into the supersaturated monosaccharide ionic liquid, wherein the mass concentration of the C5 fatty acid in the supersaturated monosaccharide ionic liquid is 10-1000g/L, adding lipase to form a reaction system according to the consumption proportion of the lipase to the C5 fatty acid of 5-500U/g, adding a drying agent into the reaction system to remove water, and enabling the C5 fatty acid to react with the monosaccharide in the presence of the lipase at the reaction temperature of 40-55 DEG C to generate C5 fatty acid monosaccharide ester; and (4) extracting and purifying the C5 fatty acid monosaccharide ester.
Description
Technical field
The present invention relates to the preparation of lipid acid monose ester, particularly relate to a kind of preparation method and the application in cigarette and cigarette of C5 lipid acid monose ester.
Background technology
Lipid acid, especially C5 carbon chain lengths lipid acid is the important fragrance matter of a class in tobacco, can in tobacco product, increase the note of vinosity, fruit and cheese sample sweet taste, and flue gas is strengthened.But in these, low carbon chain lipid acid has volatile characteristic, at Cigarette processing with while depositing, can gradually volatilize, due to cigarette when burning and sucking not only combustion zone there is high temperature, and also there is quite high temperature pyrolysis distillation zone, therefore, sharply volatilization of these acid while burning and sucking, thus the quality of cigarette smoke and the inconsequent of suction taste affected.Therefore, how improving the stability of low carbon chain lipid acid in aspiration procedure, is the popular domain of current tobacco scientific and technical personnel research.
Summary of the invention
Technical problem to be solved by this invention is: make up above-mentioned the deficiencies in the prior art, propose a kind of preparation method and the application in cigarette and cigarette of C5 lipid acid monose ester, can improve the stability of C5 lipid acid in aspiration procedure.
Technical problem of the present invention is solved by following technical scheme: a kind of preparation method of saturated fatty acid monose ester, comprises the steps:
(1) preparation mixed ionic liquid, in described mixed ionic liquid, the volume ratio of hydrophilic ionic-liquid and hydrophobic ionic liquid is 1:0.1～1:10;
(2) the monose aqueous solution of 0.1～10 times of described mixed ionic liquid volume is added in described mixed ionic liquid and mixed, at 50 ℃～60 ℃, concentrating under reduced pressure is removed undissolved monose after dewatering, and obtains over-saturation monose ionic liquid;
(3) in described over-saturation monose ionic liquid, add C5 lipid acid, mass concentration at C5 lipid acid described in described over-saturation monose ionic liquid is 10～1000g/L, the ratio that is 5～500U/g in the ratio of lipase and described C5 lipid acid consumption again adds lipase to form reaction system, in described reaction system, add siccative to dewater, under the temperature of reaction of 40～55 ℃, described lipase-catalyzed under, the reaction of described C5 lipid acid and monose generates C5 lipid acid monose ester;
(4) C5 lipid acid monose ester described in extraction and purifying.
Find after deliberation lipid acid to be combined with carbohydrate and can greatly to improve the stability of lipid acid in tobacco, utilize the regioselectivity of lipase, can from carbohydrate and lipid acid, synthesize the location-specific sugar ester of esterification easily, and reaction conditions is gentle, easy to operate, contriver studies discovery, although ionic liquid is to monose, polysaccharide has certain solvability, as glucose at hydrophilic ionic-liquid as [Bmim] [TfO] (1-butyl-3-methylimidazoium trifluoromethanesulfonate, 1-butyl-3-Methylimidazole fluoroform sulphonate) solubleness in is 4.8g/L(25 ℃), but by traditional method, monose crystal is added in hydrophilic ionic-liquid, its solubleness is still very low, be difficult to meet the needs of high conversion, when contriver also finds to carry out the synthetic C5 lipid acid monose ester of enzyme process in as [Bmim] [TfO] at single ionic liquid, thereby enzyme is lived and is reduced the recycling rate variance that causes rapidly immobilized enzyme, cost raises, be unfavorable for industrial production, and hydrophobic ionic liquid is as [Bmim] [Tf
2n] (1-butyl-3-methylimidazolium bis[(trifluoromethyl) sulfonyl] amide, the two fluoroform sulfimide salt of 1-butyl-3-Methylimidazole) in, the solubleness of monose is very little, but the stability of enzyme is higher.Also surprised discovery of contriver, if (being about to monose crystal adds and raises temperature in ionic liquid then after slow cooling to adopt traditional method to prepare over-saturation monose ionic liquid, remove undissolved monose) time, the solubleness of monose is still lower, and the solubleness of monose in ionic liquid is unstable, crystal is easily separated out, should not be for the preparation of C5 lipid acid monose ester of the present invention, and adopt the method in step of the present invention (2) to prepare over-saturation monose ionic liquid, can significantly improve the solubleness of monose in ionic liquid, and crystal is difficult for separating out.
Saturated fatty acid monose ester prepared by a kind of described preparation method application in cigarette, by the independent wiring solution-forming of described C5 lipid acid monose ester or allocate in conventional tobacco spice and be sprayed in tobacco with perfuming or reinforced mode, press the weighing scale of tobacco, the weight that adds of described C5 lipid acid monose ester is 0.0005%-0.05%.
The C5 lipid acid monose ester that the present invention obtains by aforesaid method has typical fruit flavouring, can be used in perfume industry, above-mentioned C5 lipid acid monose ester is added in cigarette shreds and is found by the test of smokeing panel test, it has obvious soft flue gas, improve flue gas drying sense, promote the effect of flue gas quality.
A cigarette, is added with the C5 lipid acid monose ester that described method obtains in described cigarette.
The present invention also tool has the following advantages: the present invention calculates with C5 lipid acid substrate, the transformation efficiency of C5 lipid acid monose ester is 20% to 95%, in the over-saturation monose ionic liquid of preparing in the present invention, by the lipase-catalyzed C5 of making lipid acid monose ester, provide a kind of new and effective biocatalytic reaction method for C5 lipid acid monose ester.
Embodiment
Below in conjunction with preferred embodiment the invention will be further described.
The preparation method who the invention provides a kind of saturated fatty acid monose ester, in one embodiment, comprises the steps:
(1) preparation mixed ionic liquid, in described mixed ionic liquid, the volume ratio of hydrophilic ionic-liquid and hydrophobic ionic liquid is 1:0.1～1:10;
(2) the monose aqueous solution of 0.1～10 times of described mixed ionic liquid volume is added in described mixed ionic liquid and mixed, at 50 ℃～60 ℃, concentrating under reduced pressure is removed undissolved monose after dewatering, and obtains over-saturation monose ionic liquid;
(3) in described over-saturation monose ionic liquid, add C5 lipid acid, mass concentration at C5 lipid acid described in described over-saturation monose ionic liquid is 10～1000g/L, the ratio that is 5～500U/g in the ratio of lipase and described C5 lipid acid consumption again adds lipase to form reaction system, in described reaction system, add siccative to dewater, under the temperature of reaction of 40～55 ℃, described lipase-catalyzed under, the reaction of described C5 lipid acid and monose generates C5 lipid acid monose ester;
(4) C5 lipid acid monose ester described in extraction and purifying.
In some preferred embodiments, under the condition of above-described embodiment, can adopt at least one in following optimum condition:
Described in step (1), volume ratio is 1:1～1:3, and under this volume ratio, the transformation efficiency of reaction is higher, and enzyme reduction alive is less, with the enzyme reclaiming, again reacts, and transformation efficiency is still higher.
Described hydrophilic ionic-liquid is that negatively charged ion is TfO
-, BF
4 -, Cl
-, Br
-, HSO
4 -, CF
3cO
2 -, DMP
-, DEP
-, DBP
-, AC
-, NO
3 -and ES
-hydrophilic ionic-liquid at least one; Described hydrophobic ionic liquid is that negatively charged ion is Tf
2n
-and PF
6 -hydrophobic ionic liquid at least one.
Preferably, described hydrophilic ionic-liquid is selected from:
1-alkyl-3-Methylimidazole fluoroform sulphonate [Cnmim] [TfO], n=0,2,4,6,8(is the 1-ethyl-3-methylimidazole fluoroform sulphonate [Emim] [TfO] when the 1-butyl-3-Methylimidazole fluoroform sulphonate [Bmim] [TfO] during n=4, n=2 for example);
1-alkyl-3-methyl imidazolium tetrafluoroborate [Cnmim] [BF
4], n=0,2,4,6,8;
1-alkyl-3-Methylimidazole villaumite [Cnmim] [Cl], n=0,2,4,6,8;
3-methyl isophthalic acid-allyl imidazole villaumite [Amim] [Cl];
Diethanolamine hydrochloride [Hdea] [Cl];
Bromination 1-alkyl-3-Methylimidazole salt ionic liquid [Rmim] [Br] (R=E, B, H that different alkyl replace; E represents ethyl, and B represents 1-butyl, and H represents 1-heptyl),
Acidic ion liquid 1-alkyl-3-Methylimidazole hydrosulfate [Cnmim] [HSO
4], n=0,2,4,6,8,
1-alkyl-3-Methylimidazole nitrate ([Cnmim] [NO
3], n=0,2,4,6,8,
1-alkyl-3-Methylimidazole trifluoroacetate [Cnmim] [CF
3cO
2], n=0,2,4,6,8,
1-ethyl-3-methylimidazole dimethyl phosphate salt [Emim] [DMP],
1,3-methylimidazole dimethyl phosphate salt [Mmim] [DMP],
1,3-diethyl imidazoles diethyl phosphoric acid salt [Eeim] [DEP],
1-ethyl-3-methylimidazole diethyl phosphoric acid salt [Emim] [DEP],
1-butyl-3-Methylimidazole dibutyl phosphate salt [Bmim] [DBP],
1-ethyl-3-methylimidazole sulfovinic acid salt [Emim] [ES],
Diethanolamine villaumite [Hdea] [Cl]
Monoethanolamine MEA BASF acetate [Hmea] [Ac],
Diethanolamine acetate [Hdea] [Ac],
Trolamine acetate [Htea] [Ac];
Described hydrophobic ionic liquid is selected from:
Two fluoroform sulfimide salt [the Bmim] [Tf of 1-butyl-3-Methylimidazole
2n], 1-alkyl-3-Methylimidazole hexafluorophosphate [Cnmim] [PF
6], n=0,2,4,6,8,10.
Described in step (2) in the monose aqueous solution, the mass concentration of monose is 50g/L～500g/L, further preferred monose mass concentration is 100g/L～400g/L, in the over-saturation monose ionic liquid preparing under this preferred concentration, solubleness and the stability of solution of monose in ionic liquid further improves.
By concentrating under reduced pressure, dewater so that massfraction≤10% of water in over-saturation monose ionic liquid described in step (2), more preferably≤2%.In over-saturation monose ionic liquid, too much moisture is unfavorable for the generation of C5 lipid acid monose ester, and under the massfraction of preferred water, the transformation efficiency of C5 lipid acid monose ester is higher.
Described C5 lipid acid can be positive valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, 2-pentenoic acid, 3-pentenoic acid, 4-pentenoic acid, 2-methyl-3-butenoic acid, 2-methyl-2-butenoic acid, 2-ethyl-2-vinylformic acid, 2, a kind of in 4-diamyl olefin(e) acid.
Described monose can be in glucose, fructose, semi-lactosi, seminose, ribose, ribodesose, wood sugar, pectinose a kind of.
In step (3), the add-on of siccative is relevant with the water-taking efficiency of siccative, and more preferably, described siccative can adopt 4A molecular sieve, and the quality that adds of 4A molecular sieve can be the 5-15% of the volume of described reaction system.
Described lipase can be selected commercialization or self-control lipase, and lipase state can be free or immobilization.The microbe-derived Candida Antarctica(antarctic candida that is selected from of lipase), Thermomyces lanuginosus aspergillus oryzae, Rhizomucor miehei rhizomucor miehei or Mucor miehei rice black wool are mould, more preferably, adopting source is the immobilized enzyme of antarctic candida, can be so that transformation efficiency further raises.
In the extraction described in step (4), it is the extracting method of this area routine, for example can be by adding solvent extraction to obtain C5 lipid acid monose ester, described solvent can be ethyl acetate, the trimethyl carbinol, ethanol etc., described purifying is the purification process of this area routine, can be for example by the method for silica gel column chromatography or macroporous resin adsorption wash-out, purifying can be so that the quality purity of C5 lipid acid monose ester be greater than 95%.
The present invention also provides C5 lipid acid monose ester prepared by the preparation method of a kind of above-mentioned arbitrary embodiment application in cigarette, by the independent wiring solution-forming of described C5 lipid acid monose ester or allocate in conventional tobacco spice and be sprayed in tobacco with perfuming or reinforced mode, press the weighing scale of tobacco, the weight that adds of described C5 lipid acid monose ester is 0.0005%-0.05%, preferably, the weight that adds of described C5 lipid acid monose ester is 0.001%-0.008%.Preferably, described C5 lipid acid monose ester is at least one in positive valeric acid glucose ester, 2-Methyl Butyric Acid glucose ester and 3 Methylbutanoic acid glucose ester.
The present invention also provides a kind of cigarette, in described cigarette, be added with the C5 lipid acid monose ester that the preparation method of above-mentioned arbitrary embodiment obtains, wherein preferably, described C5 lipid acid monose ester is at least one in positive valeric acid glucose ester, 2-Methyl Butyric Acid glucose ester and 3 Methylbutanoic acid glucose ester.
With specific embodiment, the invention will be further described below.
Embodiment mono-
By 50mL hydrophilic ionic-liquid [Bmim] [TfO] and 50mL hydrophobic ionic liquid [Bmim] [Tf
2n] mix.In mixed ionic liquid, add 400g/L D/W 50g.By glucose ion liquid mixture under 50 ℃ of rotating conditions of Rotary Evaporators concentrated water content of anhydrating to mixing liquid lower than 10%(massfraction) (with karl Fischer method, measuring), then undissolved glucose particle is separated with ionic liquid, collection of ions liquid level obtains over-saturation glucose ion liquid mixture.In 500ml tool plug triangular flask, add above-mentioned glucose ion liquid, 3 Methylbutanoic acid 8.2g, Novozyme435(to derive from Candida Antarctica) 410U, 4A molecular sieve 10g, 40 ℃ of constant-temperature table reaction 20h, press 3 Methylbutanoic acid and calculate, reaction conversion ratio is 82%.Add 500mL ethyl acetate extraction 3 times, collect ethyl acetate, ethyl acetate is gone in underpressure distillation, collects and obtains 18.4g mixture.Silicagel column on mixture be take to toluene: ethyl acetate: ethanol: water=40:30:25:1 (V/V) as eluent carries out wash-out, obtain the 3 Methylbutanoic acid glucose ester 4.2g of purifying.Collect reacted immobilized enzyme, after adding water and tetrahydrofuran (THF) to rinse, stand-by after 45 ℃ of vacuum-dryings.By above identical method, with the enzyme reclaiming, react for the second time, transformation efficiency 77%(is by 3 Methylbutanoic acid), reaction conversion ratio is 72% for the third time.
Embodiment bis-
By 90mL hydrophilic ionic-liquid [Bmim] [TfO] and 10mL hydrophobic ionic liquid [Bmim] [Tf
2n] mix.In mixed ionic liquid, add 500g/L D/W 40g.Glucose ion liquid mixture concentrated water content of anhydrating to mixing liquid under 50 ℃ of rotating conditions of Rotary Evaporators is measured with karl Fischer method lower than 2%(), then undissolved glucose particle is separated with ionic liquid, collection of ions liquid level obtains over-saturation glucose ion liquid mixture.In 500ml tool plug triangular flask, add above-mentioned glucose ion liquid, 3 Methylbutanoic acid 8.2g, Novozyme435(to derive from Candida Antarctica) 410U, 4A molecular sieve 15g, 40 ℃ of constant-temperature table reaction 20h, press 3 Methylbutanoic acid and calculate, reaction conversion ratio is 80%.Add 500mL ethyl acetate extraction 3 times, collect ethyl acetate, ethyl acetate is gone in underpressure distillation, collects and obtains 19.4g mixture.Silicagel column on mixture be take to toluene: ethyl acetate: ethanol: water=40:30:25:1 (V/V) as eluent carries out wash-out, obtain the 3 Methylbutanoic acid glucose ester 4.1g of purifying.Collect reacted immobilized enzyme, after adding water and tetrahydrofuran (THF) to rinse, stand-by after 45 ℃ of vacuum-dryings.By above identical method, with the enzyme reclaiming, react for the second time, transformation efficiency 42%(is by 3 Methylbutanoic acid), reaction conversion ratio is 18% for the third time.
From embodiment bis-, can find out, when the amount of hydrophilic ionic-liquid is during more than hydrophobic ionic liquid, primary reaction conversion ratio can reach 80%, but such mixed ionic liquid is larger to enzyme damage alive, thereby while making to carry out for the second time, react for the third time with the enzyme reclaiming, transformation efficiency is lower.
Embodiment tri-
By 10mL hydrophilic ionic-liquid [Bmim] [TfO] and 90mL hydrophobic ionic liquid [Bmim] [Tf
2n] mix.In mixed ionic liquid, add 50g/L D/W 400g.Glucose ion liquid mixture concentrated water content of anhydrating to mixing liquid under 50 ℃ of rotating conditions of Rotary Evaporators is measured with karl Fischer method lower than 5%(), then undissolved glucose particle is separated with ionic liquid, collection of ions liquid level obtains over-saturation glucose ion liquid mixture.In 500ml tool plug triangular flask, add above-mentioned glucose ion liquid, 3 Methylbutanoic acid 8.2g, Novozyme435(to derive from Candida Antarctica) 410U, 4A molecular sieve 10g, 40 ℃ of constant-temperature table reaction 20h, press 3 Methylbutanoic acid and calculate, reaction conversion ratio is 50%.Add 500mL ethyl acetate extraction 3 times, collect ethyl acetate, ethyl acetate is gone in underpressure distillation, collects and obtains 14.4g mixture.Silicagel column on mixture be take to toluene: ethyl acetate: ethanol: water=40:30:25:1 (V/V) as eluent carries out wash-out, obtain the 3 Methylbutanoic acid glucose ester 3.2g of purifying.Collect reacted immobilized enzyme, after adding water and tetrahydrofuran (THF) to rinse, stand-by after 45 ℃ of vacuum-dryings.By above identical method, with the enzyme reclaiming, react for the second time, transformation efficiency 48%(is by 3 Methylbutanoic acid), reaction conversion ratio is 47% for the third time.
Embodiment tetra-
By 25mL hydrophilic ionic-liquid [Bmim] [TfO] and 75mL hydrophobic ionic liquid [Bmim] [Tf
2n] mix.In mixed ionic liquid, add 400g/L D/W 50g.Glucose ion liquid mixture concentrated water content of anhydrating to mixing liquid under 50 ℃ of rotating conditions of Rotary Evaporators is measured with karl Fischer method lower than 10%(), then undissolved glucose particle is separated with ionic liquid, collection of ions liquid level obtains over-saturation glucose ion liquid mixture.In 500ml tool plug triangular flask, add above-mentioned glucose ion liquid, 3 Methylbutanoic acid 22g, Novozyme435(to derive from Candida Antarctica) 410U, 4A molecular sieve 10g, 40 ℃ of constant-temperature table reaction 24h, press 3 Methylbutanoic acid and calculate, reaction conversion ratio is 85%.Add 500mL ethyl acetate extraction 3 times, collect ethyl acetate, ethyl acetate is gone in underpressure distillation, collects and obtains 28.6g mixture.Silicagel column on mixture be take to toluene: ethyl acetate: ethanol: water=40:30:25:1 (V/V) as eluent carries out wash-out, obtain the 3 Methylbutanoic acid glucose ester 6.9g of purifying.Collect reacted immobilized enzyme, after adding water and tetrahydrofuran (THF) to rinse, stand-by after 45 ℃ of vacuum-dryings.By above identical method, with the enzyme reclaiming, react for the second time, transformation efficiency 81%(is by 3 Methylbutanoic acid), reaction conversion ratio is 78% for the third time.
Embodiment five
With Thermomyces lanuginosus source, Lipase TLIM carries out enzyme catalysis.With 2-Methyl Butyric Acid, replace 3 Methylbutanoic acid to press the reaction conditions of embodiment mono-, add Lipase TLIM1000U to prepare 2-Methyl Butyric Acid glucose ester under 45 ℃ of reaction conditionss, transformation efficiency (by 2-Methyl Butyric Acid) is 58%.Add 500mL trimethyl carbinol extraction 3 times, collect trimethyl carbinol layer, the trimethyl carbinol is removed in underpressure distillation, collects and obtains 14.7g mixture.Mixture is carried out to column chromatography by silicagel column in the method for embodiment mono-and be further purified, obtain the 2-Methyl Butyric Acid glucose ester 3.3g of purifying.The method of pressing embodiment mono-reclaims immobilized enzyme, and the enzyme of recovery reacts for the second time, and transformation efficiency 52%(is by 2-Methyl Butyric Acid), reaction conversion ratio is 47% for the third time.
Embodiment six
By 50mL ionic liquid [Bmim] [TfO] and 50mL ionic liquid [Bmim] [Tf
2n] mix.In mixed ionic liquid, add 400g/L fructose water solution 50g.Fructose ionic liquid mixture concentrated anhydrating to water content under 55 ℃ of rotating conditions of Rotary Evaporators measured with karl Fischer method lower than 2%(), then undissolved fructose particle is separated with ionic liquid, collection of ions liquid level obtains over-saturation fructose ionic liquid mixture.In 500ml tool plug triangular flask, add above-mentioned fructose ionic liquid, positive valeric acid 22g, Novozyme4351000U, 4A molecular sieve 15g, 50 ℃ of constant-temperature table reaction 20h, calculate by positive valeric acid, and transformation efficiency is 62%.Add 500mL ethyl acetate extraction 3 times, collect ethyl acetate, ethyl acetate is gone in underpressure distillation, collects and obtains 26.9g mixture.Mixture is carried out to column chromatography by silicagel column in the method for embodiment mono-and be further purified, obtain the positive valeric acid fructose ester 7.8g of purifying.
Embodiment seven
By 50mL ionic liquid [Bmim] [BF
4] and 50mL ionic liquid [Bmim] [PF
6] mix.In mixed ionic liquid, add 400g/L fructose water solution 50g.Fructose ionic liquid mixture concentrated anhydrating to water content under 55 ℃ of rotating conditions of Rotary Evaporators measured with karl Fischer method lower than 2%(), then undissolved fructose particle is separated with ionic liquid, collection of ions liquid level obtains over-saturation fructose ionic liquid mixture.In 500ml tool plug triangular flask, add above-mentioned fructose ionic liquid, 2,4-pentadienoic acid 22g, Novozyme4351000U, 4A molecular sieve 15g, 50 ℃ of constant-temperature table reaction 20h, calculate by 2,4-pentadienoic acid, and transformation efficiency is 58%.Add 500mL ethyl acetate extraction 3 times, collect ethyl acetate, ethyl acetate is gone in underpressure distillation, collects and obtains 25.8g mixture.Mixture is carried out to column chromatography by silicagel column in the method for embodiment mono-and be further purified, obtain 2 of purifying, 4-pentadienoic acid fructose ester 7.5g.
Embodiment eight
It is 0.5% ethanolic soln that 3 Methylbutanoic acid glucose ester after embodiment mono-purifying is made into mass concentration, adopt cigarette automatic perfume adding machine that 3 Methylbutanoic acid glucose ester solution is injected in blank cigarette equably, by cigarette quality, the add-on of 3 Methylbutanoic acid glucose ester is 0.001%-0.008%(massfraction).The test cigarette of blank cigarette and application of sample is positioned over to relative humidity (60 ± 3) %, in the environment of temperature (22 ± 2) ℃ more than balance 48h, by the group of smokeing panel test, 3 Methylbutanoic acid glucose ester perfuming cigarette is smoked panel test, using blank cigarette as blank sample, evaluate cigarette sample fragrance matter, humectation, the pungency of different perfuming amounts.Smoking result is as shown in the table.
The 3 Methylbutanoic acid glucose ester perfuming cigarette table of smokeing panel test
| Consumption | Smoking result |
| Blank | Flue gas is coarse, and dried-up assorted gas is heavier, and flue gas has dry sensation |
| 0.001% | Flue gas soften is slightly improved, and the fragrant richness of cigarette promotes, and dry sensation makes moderate progress |
| 0.003% | Flue gas soften improves obviously, and cigarette is fragrant abundant, and dry sensation improves obviously |
| 0.005% | Flue gas soften improves obviously, and cigarette is fragrant abundant, and dry sensation improves obviously |
| 0.008% | Flue gas soften improves obviously, but slightly owes clear, and flue gas is sweet |
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For those skilled in the art, without departing from the inventive concept of the premise, can also make some being equal to substitute or obvious modification, and performance or purposes identical, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. a preparation method for C5 lipid acid monose ester, is characterized in that, comprises the steps:
(1) preparation mixed ionic liquid, in described mixed ionic liquid, the volume ratio of hydrophilic ionic-liquid and hydrophobic ionic liquid is 1:0.1～1:10;
(2) the monose aqueous solution of 0.1～10 times of described mixed ionic liquid volume is added in described mixed ionic liquid and mixed, at 50 ℃～60 ℃, concentrating under reduced pressure is removed undissolved monose after dewatering, and obtains over-saturation monose ionic liquid;
(3) in described over-saturation monose ionic liquid, add C5 lipid acid, mass concentration at C5 lipid acid described in described over-saturation monose ionic liquid is 10～1000g/L, the ratio that is 5～500U/g in the ratio of lipase and described C5 lipid acid consumption again adds lipase to form reaction system, in described reaction system, add siccative to dewater, under the temperature of reaction of 40～55 ℃, described lipase-catalyzed under, the reaction of described C5 lipid acid and monose generates C5 lipid acid monose ester;
(4) C5 lipid acid monose ester described in extraction and purifying.
2. preparation method as claimed in claim 1, is characterized in that: described in step (1), volume ratio is 1:1～1:3.
3. preparation method as claimed in claim 1 or 2, is characterized in that: described hydrophilic ionic-liquid is that negatively charged ion is TfO
-, BF
4 -, Cl
-, Br
-, HSO
4 -, CF
3cO
2 -, DMP
-, DEP
-, DBP
-, AC
-, NO
3 -and ES
-hydrophilic ionic-liquid at least one; Described hydrophobic ionic liquid is that negatively charged ion is Tf
2n
-and PF
6 -hydrophobic ionic liquid at least one.
4. preparation method as claimed in claim 3, is characterized in that: described hydrophilic ionic-liquid is selected from [Cnmim] [TfO] n=0,2,4,6,8, [Cnmim] [BF
4] n=0,2,4,6,8, [Cnmim] [Cl] n=0,2,4,6,8, [Amim] [Cl], [Rmim] [Br] R=E, B, H, E represents ethyl, and B represents 1-butyl, and H represents 1-heptyl, [Cnmim] [HSO
4] n=0,2,4,6,8, [Cnmim] [NO
3] n=0,2,4,6,8, [Cnmim] [CF
3cO
2] n=0,2,4,6,8, [Emim] [DMP], [Eeim] [DEP], [Mmim] [DMP], [Emim] [DEP], [Bmim] [DBP], [Emim] [ES], [Hdea] [Cl], [Hmea] [Ac], [Hdea] [Ac], [Htea] [Ac];
Described hydrophobic ionic liquid is selected from [Bmim] [Tf
2n], [Cnmim] [PF
6] n=0,2,4,6,8,10.
5. preparation method as claimed in claim 1 or 2, is characterized in that: described in step (2), in the monose aqueous solution, the mass concentration of monose is 50g/L～500g/L.
6. preparation method as claimed in claim 1 or 2, is characterized in that: massfraction≤10% of water in over-saturation monose ionic liquid described in step (2).
7. preparation method as claimed in claim 1 or 2, it is characterized in that: described C5 lipid acid is positive valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, 2-pentenoic acid, 3-pentenoic acid, 4-pentenoic acid, 2-methyl-3-butenoic acid, 2-methyl-2-butenoic acid, 2-ethyl-2-vinylformic acid, 2 a kind of in 4-diamyl olefin(e) acid; Described monose is a kind of in glucose, fructose, semi-lactosi, seminose, ribose, ribodesose, wood sugar, pectinose.
8. preparation method as claimed in claim 1 or 2, is characterized in that: it is mould that described lipase derives from antarctic candida, aspergillus oryzae, rhizomucor miehei or rice black wool.
9. the application of the C5 lipid acid monose ester that prepared by a preparation method claimed in claim 1 in cigarette, it is characterized in that: by the independent wiring solution-forming of described C5 lipid acid monose ester or allocate in conventional tobacco spice and be sprayed in tobacco with perfuming or reinforced mode, press the weighing scale of tobacco, the weight that adds of described C5 lipid acid monose ester is 0.0005%-0.05%.
10. a cigarette, is characterized in that: in described cigarette, be added with the C5 lipid acid monose ester that method according to claim 1 obtains.
Priority Applications (1)
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Cited By (4)
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| CN103966022A (en) * | 2014-05-20 | 2014-08-06 | 河北中烟工业有限责任公司 | Mellow-sweet type spice for cigarettes |
| CN104593445A (en) * | 2015-01-21 | 2015-05-06 | 深圳大学 | Method for synthesizing sucrose fatty acid ester |
| CN104788508A (en) * | 2015-03-20 | 2015-07-22 | 深圳大学 | Synthetic method of sucrose fatty acid ester based on ionic liquid |
| CN106854225A (en) * | 2016-12-14 | 2017-06-16 | 盐城市春竹香料有限公司 | A kind of preparation method and applications of glucose ester |
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| CN102423114A (en) * | 2011-07-25 | 2012-04-25 | 红塔烟草(集团)有限责任公司 | Low-tar cigarette aroma compensation method |
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| CN102423114A (en) * | 2011-07-25 | 2012-04-25 | 红塔烟草(集团)有限责任公司 | Low-tar cigarette aroma compensation method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103966022A (en) * | 2014-05-20 | 2014-08-06 | 河北中烟工业有限责任公司 | Mellow-sweet type spice for cigarettes |
| CN104593445A (en) * | 2015-01-21 | 2015-05-06 | 深圳大学 | Method for synthesizing sucrose fatty acid ester |
| CN104788508A (en) * | 2015-03-20 | 2015-07-22 | 深圳大学 | Synthetic method of sucrose fatty acid ester based on ionic liquid |
| CN106854225A (en) * | 2016-12-14 | 2017-06-16 | 盐城市春竹香料有限公司 | A kind of preparation method and applications of glucose ester |
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