CN103467535B - A kind of humectant for smoke 1-O-hydroxyethyl-D-Fructose and preparation method thereof - Google Patents
A kind of humectant for smoke 1-O-hydroxyethyl-D-Fructose and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of humectant for smoke 1-O-hydroxyethyl-D-Fructose, its structural formula is as follows:
Description
Technical field
The invention belongs to humectant technical field, be specifically related to a kind of humectant for smoke 1-O-hydroxyethyl-D-Fructose and preparation method thereof.
Background technology
Humectant is in cigarette manufacturing processed, in order to strengthen the resist processing of tobacco, reducing rough broken, the loss adding man-hour, keeping toughness and moisture simultaneously, and a kind of additive added.The main component of tradition humectant is generally the polyhydroxy substance such as glycerine and propylene glycol, the main purpose of this type of humectant is the water ratio maintaining pipe tobacco in the course of processing, improve the resist processing of pipe tobacco, the object of pipe tobacco moisturizing is mainly reached according to polar group wherein and the avidity of water molecules, but, this humectant binding ability is more weak, can not play good humectation effect, and to the maintenance of finished cigarettes water ratio, suck comfort level improvement effect also not ideal; In addition, these humectants mainly rely on its water absorbability to produce humectation effect, but without moisture effect to tobacco; In addition, glycerine price is not only relatively high, and more importantly its usage quantity can not be excessive, otherwise can have a strong impact on the mouthfeel of sucking.Have precipitation during the humectant long storage time of the poor Xylitol of effect, glucitols, temperature is lower easily solidifies, be therefore not easy to production and application.
Summary of the invention
The object of the present invention is to provide a kind of humectant for smoke 1-O-hydroxyethyl-D-Fructose, another object of the present invention is to the preparation method that this humectant is provided.
For achieving the above object.The present invention adopts following technical scheme:
A kind of humectant for smoke 1-O-hydroxyethyl-D-Fructose, its structural formula is as follows:
。
The preparation method of described humectant for smoke 1-O-hydroxyethyl-D-Fructose, comprises the following steps:
(1) preparation of 1-O-hydroxyethyl-2,3:4,5-bis--O-isopropylidene-α-D-pyranofructose (II)
Under gas shield, 1-O-carboxymethyl-2,3:4, the 5-bis--O-isopropylidene-α-D-pyranofructose tert-butyl ester (I) is dissolved in tetrahydrofuran (THF), then cools, at 0-10 DEG C, slowly add LiAlH
4, then 10-25 DEG C of reaction 2.5-4.5h, then dripping volume percent is that the ethyl acetate aqueous solution of 30-70% terminates reaction, and filtering-depositing, concentrating under reduced pressure obtain intermediate product (II); Feed ratio adds tetrahydrofuran (THF), the LiAlH4 of 0.004-0.0055mol, the ethyl acetate aqueous solution meter of 2-4mL of 8-15mL according to every 1 gram of raw material (I).Tlc (TLC) can be adopted in reaction process to monitor, and developping agent is the mixed solvent (V be made up of sherwood oil and ethyl acetate
sherwood oil: V
ethyl acetate=3:2)
(2) preparation of 1-O-hydroxyethyl-D-Fructose (III)
After intermediate product (II), storng-acid cation exchange resin and water being mixed, at 50-80 DEG C, react 5.5-7.5h, through filtering, concentrating to obtain target product (III) after reaction terminates; Wherein, feed ratio adds 4-7g storng-acid cation exchange resin and 4-7g water meter according to every 1 gram of intermediate product (II).Tlc (TLC) can be adopted in reaction process to monitor, and developping agent is the mixed solvent (V be made up of propyl carbinol, glacial acetic acid and water
propyl carbinol: V
glacial acetic acid: V
water=5:1:1).
In aforesaid method, preferably, gases used in step (1) is nitrogen; The volume percent of ethyl acetate aqueous solution used is 50%.
In aforesaid method, preferably, LiAlH is added
4time temperature controlled by ice-water bath.
Synthetic route of the present invention is as follows:
The present invention for starting raw material, successfully synthesizes a kind of humectant for smoke 1-O-hydroxyethyl-D-Fructose (III) with 1-O-carboxymethyl-2,3:4, the 5-bis--O-isopropylidene-α-D-pyranofructose tert-butyl ester (I).By the test of physics humid keeping performance and inherent sensory quality assessment, find that it has good physics humectation effect to cigarette, and cigarette pungency and assorted gas can be reduced, improve the mellow and full sense of cigarette smoke and comfort level.Raw of the present invention is cheap and easy to get, easy and simple to handle, and gained target product is obvious to tobacco product effect, has industrial value and the bright prospects applied significantly.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of intermediate product (II);
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of intermediate product (II);
Fig. 3 is the carbon-13 nmr spectra figure of intermediate product (II);
Fig. 4 is the infrared spectrogram of target product (III);
Fig. 5 is the high resolution mass spectrum figure of target product (III);
Fig. 6 is the hydrogen nuclear magnetic resonance spectrogram of target product (III);
Fig. 7 is the carbon-13 nmr spectra figure of target product (III);
Fig. 8 is the physics humectation effect contrast figure of embodiment 3 gained target product (III), sorbyl alcohol, glycerine, propylene glycol and D-Fructose.
Embodiment
Below by specific embodiment, the present invention is further explained, but protection scope of the present invention is not limited in this.
Be below portion of reagent used and instrument in embodiment.
1-O-carboxymethyl-2,3:4, the 5-bis--O-isopropylidene-α-D-pyranofructose tert-butyl ester (more than 99%, China Tobacco Henan Industrial Co., Ltd technique center); Dehydrated alcohol, sherwood oil, propyl carbinol, glacial acetic acid, LiAlH
4(AR, Tianjin Kai Tong chemical reagent company limited); Ethyl acetate (AR, Yantai City is Chemical Co., Ltd. in pairs); Tetrahydrofuran (THF) (THF) (AR, Chemical Reagent Co., Ltd., Sinopharm Group); Amberlite IR-120 (H) ion exchange resin (Alfa Aesar).
Thermo Nicolet Avatar370 infrared spectrometer (Nicolet company of the U.S.); Bruker Avance AMX-400 nuclear magnetic resonance spectrometer (Bruker company of the U.S.); BS200SWE1 type electronic balance (sensibility reciprocal: 0.0001g, Beijing match Doris balance company limited); R-215 type Rotary Evaporators (BUCHI company of Switzerland); V-700 vacuum pump (BUCHI company of Switzerland); DLSB-20/60 DEG C of subcooling recycle pump (Shanghai Mei Qiang plant and instrument company limited); KDM type regulating temp. electrothermal cover (Shandong Hua Lu electric heating Instrument Ltd.).
embodiment 1
The preparation method of 1-O-carboxymethyl-D-fructofuranose, it comprises the steps:
(1) preparation of 1-O-hydroxyethyl-2,3:4,5-bis--O-isopropylidene-α-D-pyranofructose (II)
Take 1-O-carboxymethyl-2; 3:4; 5-bis--O-isopropylidene-α-D-pyranofructose the tert-butyl ester (I) 6.0g is in 250mL there-necked flask; add the tetrahydrofuran (THF) (THF) of 48mL; magnetic agitation makes it dissolve; then logical nitrogen protection, ice-water bath is cooled to less than 10 DEG C (to be advisable between 0-10 DEG C), then slowly adds LiAlH
40.024mol, raised temperature also reacts 2.5h at 10 DEG C, and TLC monitors whole reaction process (V
sherwood oil: V
ethyl acetate=3:2), then slowly drip 12mL volume half proportion by subtraction be 70% ethyl acetate aqueous solution terminate reaction, filtering-depositing, concentrating under reduced pressure obtain water white transparency thick liquid (II) 3.45g, and productive rate is 70.65%.
(2) preparation of 1-O-hydroxyethyl-D-Fructose (III)
1g product (II), 4g Amberlite IR-120 storng-acid cation exchange resin and 4g water is added respectively in the 50mL round-bottomed flask that reflux condensing tube is housed, temperature remains 50 DEG C, magnetic agitation reaction 5.5h, with TLC monitoring in reaction process, developping agent forms mixed solvent (V by propyl carbinol, glacial acetic acid and water
propyl carbinol: V
glacial acetic acid: V
water=5:1:1).Reaction terminate rear reaction solution after filtration, concentrated obtain the thick target product of 0.446g water white transparency (III), productive rate is 60.58%.
embodiment 2
The preparation method of 1-O-carboxymethyl-D-fructofuranose, it comprises the steps:
(1) preparation of 1-O-hydroxyethyl-2,3:4,5-bis--O-isopropylidene-α-D-pyranofructose (II)
Take 1-O-carboxymethyl-2; 3:4; 5-bis--O-isopropylidene-α-D-pyranofructose the tert-butyl ester (I) 6.0g is in 250mL there-necked flask; add the tetrahydrofuran (THF) (THF) of 60mL; magnetic agitation makes it dissolve; then logical nitrogen protection, ice-water bath is cooled to less than 10 DEG C (to be advisable between 0-10 DEG C), then slowly adds LiAlH
40.03mol, raised temperature also reacts 3.5h at 16 DEG C, and TLC monitors whole reaction process (V
sherwood oil: V
ethyl acetate=3:2), then slowly drip 19mL volume percent be 50% ethyl acetate aqueous solution terminate reaction, filtering-depositing, concentrating under reduced pressure obtain water white transparency thick liquid (II) 4.40g, and productive rate is 90.26%.
(2) preparation of 1-O-hydroxyethyl-D-Fructose (III)
1g product (II), 6g Amberlite IR-120 storng-acid cation exchange resin and 6g water is added respectively in the 50mL round-bottomed flask that reflux condensing tube is housed, temperature remains 65 DEG C, magnetic agitation reaction 5h, with TLC monitoring in reaction process, developping agent forms mixed solvent (V by propyl carbinol, glacial acetic acid and water
propyl carbinol: V
glacial acetic acid: V
water=5:1:1).Reaction terminate rear reaction solution after filtration, concentrated obtain the thick target product of 0.663g water white transparency (III), productive rate is 89.92%.
embodiment 3
The preparation method of 1-O-carboxymethyl-D-fructofuranose, it comprises the steps:
(1) preparation of 1-O-hydroxyethyl-2,3:4,5-bis--O-isopropylidene-α-D-pyranofructose (II)
Take 1-O-carboxymethyl-2; 3:4; 5-bis--O-isopropylidene-α-D-pyranofructose the tert-butyl ester (I) 6.0g is in 250mL there-necked flask; add the tetrahydrofuran (THF) (THF) of 90mL; magnetic agitation makes it dissolve; then logical nitrogen protection, ice-water bath is cooled to less than 10 DEG C (to be advisable between 0-10 DEG C), then slowly adds LiAlH
40.033mol, raised temperature also reacts 5h at 25 DEG C, and TLC monitors whole reaction process (V
sherwood oil: V
ethyl acetate=3:2), then slowly drip 24mL volume percent be 30% ethyl acetate aqueous solution terminate reaction, filtering-depositing, concentrating under reduced pressure obtain water white transparency thick liquid (II) 4.38g, and productive rate is 89.72%.
(2) preparation of 1-O-hydroxyethyl-D-Fructose (III)
1g product (II), 7g Amberlite IR-120 storng-acid cation exchange resin and 7g water is added respectively in the 50mL round-bottomed flask that reflux condensing tube is housed, temperature remains 80 DEG C, magnetic agitation reaction 7.5h, with TLC monitoring in reaction process, developping agent forms mixed solvent (V by propyl carbinol, glacial acetic acid and water
propyl carbinol: V
glacial acetic acid: V
water=5:1:1).Reaction terminate rear reaction solution after filtration, concentrated obtain the thick target product of 0.554g water white transparency (III), productive rate is 75.13%.
(1) structural characterization of intermediate product and target product
By infrared spectra (IR), proton nmr spectra (
1h-NMR), carbon-13 nmr spectra (
13c-NMR) carry out structural characterization to embodiment gained intermediate product (II) and target product (III) respectively, in addition, utilize the result of high resolution mass spectrum (HR-MS) to target product (III) to do further sign, concrete outcome is as follows.
1, the structural characterization of intermediate product (II)
(1) infrared spectra
Adopt U.S. Nicolet company's T hermo Nicolet Avatar370 type infrared spectrometric analyzer to analyze to synthesized intermediate product (II), the results are shown in Figure 1.As shown in the figure, 3490.40cm
-1for the stretching vibration of hydroxyl, describe the existence of hydroxyl; 2988.98cm
-1and 2936.80cm
-1for saturated hydrocarbyl C-H stretching vibration, 1740.49cm
-1and 1642.92cm
-1the stretching vibration of non-hydrogen saturated carbon, 1252.21cm
-1, 1209.10cm
-1, 1119.16cm
-1and 1070.00cm
-1for the coupling of C-O-C key chattering.In sum, therefore, the structure of this infrared spectra known and intermediate product (II) matches.
(2) proton nmr spectra
Adopt U.S. Bruker company Bruker Avance AMX-400 type nuclear magnetic resonance analyser to analyze to synthesized intermediate product (II), obtain product
1h-NMR collection of illustrative plates (CDCl
3for solvent) as shown in Figure 2.
1h-NMR spectrum is without obvious Interference Peaks, and by low field to High-Field, integration letter is than being 1:1:1:1:6:1:1:3:3:3:3, and its digital sum is consistent with hydrogen atom number in II molecular formula, therefore integration ratio equals the ratio of proton number.δ: 4.588-4.614ppm is H on D-Fructose ring
4with H on the carbon atom of ortho position
3and H
5coupling and the quartet to split point, its J
34=0.6Hz, J
54=2.0Hz, δ=4.601ppm; 4.370ppm and 4.364ppm is H
3with H on the carbon atom of ortho position
2and H
4the doublet that coupling is split point, its J
43=0.6Hz, δ=4.367ppm; 4.254ppm and 4.234ppm is H
5with H on the carbon atom of ortho position
4with two H
6coupling and the doublet to split point, its J
45=2.0Hz, δ=4.244ppm; 3.888-3.924ppm be a H on D-Fructose ring
6with another H
6and with the H on the carbon atom of ortho position
5the quartet that coupling is split point, its J
56=0.4Hz, J
6 ' 6=3.2Hz, δ=3.906ppm; 3.775-3.661ppm be another H
6with H
5, H
6the peak that coupling is split point, with two H
1the peak that mutual coupling is split point and two H
8with a H
7the peak that mutual coupling is split point, 11 heavy peaks of the overlapped formation in peak and peak, its J
66 '=3.3Hz; 3.600ppm and 3.574ppm is another H
7with two H
8and H
7it is bimodal that mutual coupling is split point, its J=2.6Hz, δ=3.587ppm; 2.820ppm is the unimodal of hydroxyl hydrogen in hydroxyethyl; 1.347-1.541ppm is four methyl, 12 hydrogen atoms on two isopropylidenes, due on connected carbon atom all without hydrogen atom, therefore all formed unimodal.Described in above proton nmr spectra, can think that the chemical structure of this material and intermediate product (II) is coincide.
(3) carbon-13 nmr spectra
Fig. 3 is synthesized intermediate product (II)
13c-NMR, 14 the spectrum peaks provided in figure represent the carbon atom that in molecule, 14 kinds of chemical environments are different, judge that δ is simple than being 1:1:1:1:1:1:1:1:1:1:1:1:1:1 to High-Field carbon atom number by low field according to spectral strength, its digital sum is 14, consistent with carbon atom number in II molecular formula.Tentatively carbon can be attributed to by figure: 108.928ppm and 108.421ppm is quaternary carbon atom on two isopropylidenes, and 102.609ppm is C
2, 73.313ppm is C
1, 73.090ppm is C
7, 70.763ppm is C
3, 70.597ppm is C
4, 70.116ppm is C
6, 61.426ppm is C
5, 60.953ppm is C
8, 4 methyl carbon of 26.465ppm, 25.729ppm, 25.192ppm and 23.911ppm difference two isopropylidenes.From the above mentioned, this
13the structure of the substantially same intermediate product (II) of C-NMR is coincide.
In sum, in conjunction with infrared spectra (IR), proton nmr spectra (
1h-NMR), carbon-13 nmr spectra (
13c-NMR) can determine that gained compound is intermediate product (II).
2, the structural characterization of target product (III)
(1)
infrared spectra
Adopt U.S. Nicolet company's T hermo Nicolet Avatar370 type infrared spectrometric analyzer to analyze to synthesized target product (III), the results are shown in Figure 4.As seen from the figure, 3389.25cm
-1for the hydroxyl stretching vibration of associated state, describe the existence of hydroxyl.1234.49cm
-1, 1121.15cm
-1, 1038.81cm
-1for the coupling of C-O-C key chattering.From the above mentioned, the structure of this infrared spectra known and target product (III) matches.
(2)
high resolution mass spectrum
Because intermediate product (III) Polarity comparision is strong, and more responsive to ratio of specific heat, therefore adopt electric spray ion source (ESI) high resolution mass spec (HR-MS) to carry out mass spectroscopy (high resolution mass spectrometer Exactive Orbitrap, Thermo company of the U.S.).Solvent selects the methanol aqueous solution of 50% to be moving phase, the results are shown in Figure 5.
By to its positive ion mode map analysis, sample molecule quasi-molecular ions [M+Na] can be obtained
+be 247.19791, adding sodium molecule formula is C
8h
16o
7na, can judge that its quasi-molecule is C
8h
16o
7, its relative molecular weight is 224.20814, and the Theoretical molecular formula of target product (III) is C
8h
16o
7, its theoretical Mr 224.20844, therefore, sample molecule elementary composition is consistent with the elementary composition of target product (III).
(3)
proton nmr spectra
Analyzed by nuclear magnetic resonance analyser, obtain product
1h-NMR spectrogram (D
2o is solvent), see Fig. 6.Because target product (III) is made up of 1-O-hydroxyethyl-α-D-fructofuranose and 1-O-hydroxyethyl-beta-D-fructofuranose, so its
1h-NMR is comparatively complicated, cannot belong to one by one.And same target product (III)
1h-NMR compares, III
1the unimodal disappearance of methyl hydrogen that in H-NMR, High-Field place isopropylidene contains, illustrates that isopropylidene does not exist; The chemical shift of overall hydrogen spectrum is all obvious moves to High-Field, also show sloughing of isopropylidene.
(4)
carbon-13 nmr spectra
Fig. 7 is the carbon-13 nmr spectra of this target product (III), 24 the spectrum peaks provided in figure represent the carbon atom that in molecule, 24 kinds of chemical environments are different, therefore the carbon atom of 24 different chemical displacements is had in the bright target product of this chart (III), in composition graphs, the charateristic avsorption band of 3 carbonyls that low field place occurs, tentatively can infer that this material is made up of the isomers of 3 kinds of target products (III); All containing 8 carbon atoms in three's chemical structure, sum is just 24 carbon atoms, consistent with the carbon atom number shown in spectrogram.And, according to these 3 kinds of isomers anomeric carbon (i.e. C
2) chemical shift be respectively 103.496ppm, 99.780ppm and 96.531ppm, can think that this material is made up of three kinds of compounds of a kind of five-ring furan structure and two kinds of six-ring pyran structure, the former may be 1-O-hydroxyethyl-D-fructofuranose, cannot judge its configuration, the latter should be respectively 1-O-hydroxyethyl-Beta-D-Fructopyranose and 1-O-hydroxyethyl-α-D-pyranofructose.Carbon atom roughly can be belonged to by figure, in 1-O-hydroxyethyl-D-furans seminose, carbon atom is attributed to: chemical shift 103.496ppm is C
2, 83.608ppm is C
5, 77.998ppm is C
3, 69.402ppm is C
7, 69.106ppm is C
4, 66.140ppm is C
1, 63.523ppm is C
6, 61.833ppm is C
8.1-O-hydroxyethyl-D-pyranofructose, beta configuration: chemical shift 99.780ppm is C
2, 82.022ppm is C
5, 77.507ppm is C
3, 69.361ppm is C
7, 68.276ppm is C
4, 65.995ppm is C
1, 63.233ppm is C
6and 60.833ppm is C
8; α-configuration: chemical shift 96.531ppm is C
2, 81.585ppm is C
5, 75.070ppm is C
3, 69.310ppm is C
7, 68.215ppm is C
4, 65.802ppm is C
1, 62.899ppm is C
6and 59.959ppm is C
8.
In sum, in conjunction with infrared spectra (IR), high resolution mass spec (HR-MS), proton nmr spectra (
1h-NMR) and carbon-13 nmr spectra (
13c-NMR) can determine that gained compound is 1-O-hydroxyethyl-D-Fructose.
(2) 1-O-hydroxyethyl-D-Fructose (III) applied research in tobacco
1, the physics humid keeping performance test of target product (III)
For investigating target product (III) to the physics humid keeping performance of cigarette, with the blank cigarette of " Bright Yellow " brand for carrier, embodiment 3 gained target product (III) same to propylene glycol, glycerine, D-Fructose are carried out together with sorbyl alcohol the research of physics humid keeping performance contrast test respectively, be mixed with the above-claimed cpd aqueous solution that massfraction is 10% respectively.First 1000g is mixed that blank cigarette shreds is placed in temperature 22 ± 1 DEG C, relative humidity 60 ± 2% environment balances 48h.Then equivalent takes 6 parts of pipe tobaccos, every part of 100g, evenly applies the above-mentioned polyol aqueous solution of 2g respectively respectively in five parts of pipe tobaccos, and contrasting blank sample is that pipe tobacco applies 2g water.Then 6 parts of pipe tobaccos are placed in 22 ± 1 DEG C respectively, investigate it under the environment of relative humidity 40 ± 2% and separate wet process, and the change of instant water ratio is analyzed, investigate its physics humectation effect.The physics humid keeping performance effect of target product (III), propylene glycol, glycerine, D-Fructose and sorbyl alcohol is shown in Fig. 8.
As seen from Figure 8, the pipe tobacco of interpolation target product (III), propylene glycol, glycerine, D-Fructose and sorbyl alcohol five kinds of polyols is compared with blank pipe tobacco, moisture loss speed is slower, this is that hydrophilic radical hydroxyl contained by polyol can form hydrogen bond with water and be fettered by water, delay scattering and disappearing of moisture, improve the physics humid keeping performance of pipe tobacco; The physics humid keeping performance wherein adding target product (III) is best, is secondly propylene glycol and glycerine, is finally D-Fructose and sorbyl alcohol.
2, the sense organ humid keeping performance test of target product (III)
Make solvent with 20% aqueous ethanolic solution, target product (III) is made into the solution of massfraction 1%.Get the above-mentioned solution containing target product III of 0.100g, 0.500g, 2.500g, 5.000g, 10.000g, 15.000g and 20.000g respectively, then evenly spray is added in the blank cigarette shreds of 100g " Bright Yellow " brand of seven parts of non-flavoring and casings, roll, respectively pick out 100 same weight cigarette, be placed in temperature 22 DEG C ± 1 DEG C, balance 48h in the climatic chamber of humidity 60% ± 2%, smoke panel test.Control sample is the blank cigarette of " Bright Yellow " brand, and control sample balances 48h equally under same temperature, humidity condition.
The perfuming smoking result of table 1 intermediate product (III)
| iII addition (‰) | smoking result |
| 0.01 | flue gas slightly softens, and other effect is not obvious. |
| 0.05 | flue gas slightly softens, and comfortable taste slightly promotes |
| 0.25 | flue gas slightly becomes mellow and full, soft, and comfortable taste slightly promotes, and assorted gas is in a slight decrease. |
| 0.50 | flue gas obviously becomes mellow and full, soft, and comfortable taste slightly promotes, assorted gas and pungency in a slight decrease. |
| 1.00 | flue gas obviously becomes mellow and full, soft, and comfortable taste promotes, and assorted gas and pungency obviously reduce. |
| 1.5 | flue gas obviously becomes mellow and full, soft, and comfortable taste promotes, and assorted gas obviously reduces, but spine sense slightly increases, and concentration slightly reduces. |
| 2.00 | flue gas obviously becomes mellow and full, soft, and comfortable taste promotes, and assorted gas obviously reduces, but spine sense obviously increases, and concentration reduces comparatively obvious. |
Table 1 result shows, target product (III) Main Function to cigarette shows as and makes flue gas obviously become mellow and full, soft, and comfortable taste promotes, and assorted gas reduces and pungency reduces.When target product (III) consumption is less, it is not clearly to cigarette effect; When its consumption is more than 1 ‰, occur that spine sense increases, the phenomenon that concentration reduces; When its consumption is 1 ‰, sucking quality is best.Therefore, best results when adding 0.1g target product III in 100g " Bright Yellow " brand cigarette, namely optimum consumption is 1 ‰.
Claims (6)
1. humectant for smoke 1-O-hydroxyethyl-D-Fructose, is characterized in that, its structural formula is as follows:
。
2. the preparation method of humectant for smoke 1-O-hydroxyethyl-D-Fructose described in claim 1, is characterized in that, comprise the following steps:
(1) preparation of 1-O-hydroxyethyl-2,3:4,5-bis--O-isopropylidene-α-D-pyranofructose (II)
Under gas shield, 1-O-carboxymethyl-2,3:4, the 5-bis--O-isopropylidene-α-D-pyranofructose tert-butyl ester (I) is dissolved in tetrahydrofuran (THF), at 0-10 DEG C, adds LiAlH
4, then 10-25 DEG C of reaction 2.5-4.5h, then dripping volume percent is that the ethyl acetate aqueous solution of 30-70% terminates reaction, through aftertreatment intermediate product (II); Feed ratio adds the tetrahydrofuran (THF) of 8-15mL, the LiAlH of 0.004-0.0055mol according to every 1 gram of raw material (I)
4, 2-4mL ethyl acetate aqueous solution meter;
(2) preparation of 1-O-hydroxyethyl-D-Fructose (III)
After intermediate product (II), storng-acid cation exchange resin and water being mixed, at 50-80 DEG C, react 5.5-7.5h, through processing to obtain target product (III) after reaction terminates; Wherein, feed ratio adds 4-7g storng-acid cation exchange resin and 4-7g water meter according to every 1 gram of intermediate product (II).
3. the preparation method of humectant for smoke 1-O-hydroxyethyl-D-Fructose as claimed in claim 2, it is characterized in that, gases used in step (1) is nitrogen; The volume percent of ethyl acetate aqueous solution used is 50%.
4. the preparation method of humectant for smoke 1-O-hydroxyethyl-D-Fructose as described in Claims 2 or 3, is characterized in that, add LiAlH
4time temperature controlled by ice-water bath.
5. compound
as the application of humectant for smoke.
6. apply as claimed in claim 5, it is characterized in that: addition is 0.001-0.1%.
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| US5139034A (en) * | 1990-11-15 | 1992-08-18 | Philip Morris Incorporated | Smoking compositions containing a menthol-release additive |
| JP3569432B2 (en) * | 1998-02-02 | 2004-09-22 | 辰馬本家酒造株式会社 | Method for producing α-D-glucopyranosylglycerols and use thereof |
| CN102311465B (en) * | 2011-09-05 | 2014-02-26 | 川渝中烟工业有限责任公司 | Monosaccharide geraniol carbonate monoester compound and preparation method and application thereof |
| CN102796146B (en) * | 2012-08-02 | 2014-05-14 | 河南中烟工业有限责任公司 | Humectant for cigarettes and preparation method thereof |
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Address after: 450000 Yulin South Road, Henan, Zheng Dong, No. 16 South Road, Zhengzhou Patentee after: China Tobacco Henan Industrial Co., Ltd. Patentee after: Zhengzhou Tobacco Research Institute of CNTC Address before: 450000 Zhengzhou agricultural road, Henan, No. 29 Patentee before: China Tobacco Henan Industrial Co., Ltd. Patentee before: Zhengzhou Tobacco Research Institute of CNTC |