CN104311608A - Hydrophilic aroma-enhancing humectant Mal-Hyp for tobacco, preparation method and application of humectant - Google Patents
Hydrophilic aroma-enhancing humectant Mal-Hyp for tobacco, preparation method and application of humectant Download PDFInfo
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- CN104311608A CN104311608A CN201410586148.8A CN201410586148A CN104311608A CN 104311608 A CN104311608 A CN 104311608A CN 201410586148 A CN201410586148 A CN 201410586148A CN 104311608 A CN104311608 A CN 104311608A
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- 0 C*(C[C@@](C(*)*1)O)*1OC(C(*)*[C@@](C1O)*(C)=C)=C1N=O Chemical compound C*(C[C@@](C(*)*1)O)*1OC(C(*)*[C@@](C1O)*(C)=C)=C1N=O 0.000 description 2
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Abstract
The invention belongs to the technical field of humectants for tobacco and particularly relates to a hydrophilic aroma-enhancing humectant Mal-Hyp for tobacco, a preparation method and an application of the humectant. The structural formula of the Mal-Hyp is shown in a formula in the specification. According to the invention, physical humidifying performance test and interior sensory quality of the compound are evaluated, discovering that the humectant plays a role of remarkably improving the physical humidifying performance of cut tobacco and meanwhile has a remarkable improving effect to sensory quality of tobacco, so that the irritation and miscellaneous odors are reduced and the mellow and full sense of the smoke of cigarettes is enhanced.
Description
technical field
The invention belongs to humectant for smoke technical field, be specifically related to a kind of novel hydrophilic type fragrance-enhancing tobacco humectant Mal-Hyp, preparation method and application thereof.
background technology
Along with people are to the attention gradually of smoking and health problem, while reducing tar content in cigarette further, cigarette comfortableness is deteriorated, embody a concentrated reflection of moisture in cut tobacco scatter and disappear fast, main flume moisture is on the low side, pungency is bigger than normal, oral cavity is dry and phlegm is many etc.At present, in China's cigarette, a large amount of humectant used mainly contains propylene glycol, sorbyl alcohol etc., use this type of humectant can improve the water ratio of pipe tobacco in the course of processing and pipe tobacco degrading resistance property, but above-mentioned humectant to the maintenance of cigarette rags water ratio and the improvement of sensory comfort unsatisfactory.
Summary of the invention
The object of the invention is to provide a kind of novel hydrophilic type fragrance-enhancing tobacco humectant Mal-Hyp, preparation method and application thereof.
For achieving the above object, the present invention adopts following technical scheme:
A kind of hydrophilic fragrance-enhancing tobacco humectant Mal-Hyp, its structural formula is as follows:
。
The preparation method of described hydrophilic fragrance-enhancing tobacco humectant Mal-Hyp, it comprises the steps:
By the 16-45min that refluxes under 73-90 DEG C of condition after maltose, anhydrous methanol, dimethyl formamide or mixed with propylene glycol, then add oxyproline again to reflux 16-45min, finally add strong-acid ion exchange resin and kaempferol back flow reaction 1.5-9h, be separated and recrystallization and get final product through silica gel column chromatography after reaction terminates; Wherein, feed ratio adds 0.146-0.364 gram of oxyproline, 0.160-0.802 gram kaempferol, 0.028-0.066 gram strong-acid ion exchange resin, 1.6-2.9mL anhydrous methanol, 1.3-4.0mL dimethyl formamide or propylene glycol meter according to every 1 gram of maltose.
Concrete, column chromatography for separation elutriant used is the mixed solution of propyl carbinol, glacial acetic acid and water composition, and the volume ratio of three is 4:2:1, and developer is ethanol solution of ninhydrin.
Described Mal-Hyp is as the application of fragrance-enhancing tobacco humectant in cigarette.
The synthetic route of the present invention's design is as follows:
。
The compounds of this invention Mal-Hyp is Maillard reaction intermediate, and be a kind of aroma compounds of diving, its split product mostly is furanone etc., obviously can increase the fragrant and sweet of tobacco and baking perfume.In addition, itself contain a large amount of hydrophilic radical, it can be used as fragrance-enhancing tobacco humectant still rare at present.
compared to the prior art, beneficial effect of the present invention:
1) the present invention is starting raw material with maltose first, is catalyzer, take kaempferol as inhibitor, react with oxyproline, successfully synthesize a kind of Maillard reaction intermediate-Mal-Hyp, study and determine synthesis technology condition and preferred plan with solid acid.The method technique is simple, raw material is easy to get, productive rate is higher, is applicable to suitability for industrialized production.
2) the present invention develops a kind of novel hydrophilic type compound, first Mal-Hyp is applied in cigarette as fragrance-enhancing tobacco humectant, 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 comfortableness.
3) advantage of the present invention: according to existing document analysis, the synthesis about Mal-Hyp has and rarely has report, and this route has the advantages such as raw material is easy to get, easy and simple to handle, productive rate significantly improves.Target product Mal-Hyp of the present invention is obvious to the action effect of tobacco product, the bright prospects therefore having significant industrial application value He apply.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of target product Mal-Hyp;
Fig. 2 is the high resolution mass spectrum figure of target product Mal-Hyp;
Fig. 3 is the carbon-13 nmr spectra figure of target product Mal-Hyp.
Embodiment
Below by way of specific embodiment, the present invention is described in detail, but protection scope of the present invention is not limited thereto.
Be below portion of reagent used in embodiment and instrument.
Maltose, oxyproline (99%, Aladdin chemical reagents corporation); Kaempferol (HPLC level, French Extrasynthese company); Anhydrous methanol, dehydrated alcohol, dimethyl formamide, propyl carbinol, glacial acetic acid (AR, Tianjin Kai Tong chemical reagent company limited); Amberlite IR-120 (H) ion exchange resin (Alfa Aesar); Silica gel (chemical pure, Qingdao Marine Chemical Co., Ltd.).
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
A preparation method of hydrophilic fragrance-enhancing tobacco humectant Mal-Hyp, it comprises the steps:
1 gram of maltose, 1.3mL dimethyl formamide and 2.9mL anhydrous methanol is added in the there-necked flask with thermometer, prolong, reflux 16min under 73 DEG C of conditions, then add 0.146 gram of oxyproline again to reflux 16min, finally add 0.028 gram of strong-acid ion exchange resin and 0.160 gram of kaempferol back flow reaction 1.6h, after reaction terminates, obtain white crystalline target product Mal-Hyp 0.344 gram through silica gel column chromatography separation and recrystallization; Wherein, column chromatography for separation elutriant used is the mixed solution of propyl carbinol, glacial acetic acid and water composition, and the volume ratio of three is 4:2:1, and developer is ethanol solution of ninhydrin; Recrystallization solvent for use is volume ratio is the dehydrated alcohol of 1:1 and the mixing solutions of anhydrous methanol.
embodiment 2
A preparation method of hydrophilic fragrance-enhancing tobacco humectant Mal-Hyp, it comprises the steps:
1 gram of maltose, 3.7mL dimethyl formamide, 2.0mL anhydrous methanol is added in the there-necked flask with thermometer, prolong, reflux 30min under 86 DEG C of conditions, then add 0.352 gram of oxyproline again to reflux 30min, finally add 0.05 gram of strong-acid ion exchange resin and 0.063 gram of kaempferol back flow reaction 5h, after reaction terminates, obtain white crystalline target product 0.872 gram through silica gel column chromatography separation and recrystallization.Wherein, the operating process of column chromatography for separation and recrystallization is with embodiment 1.
embodiment 3
A preparation method of hydrophilic fragrance-enhancing tobacco humectant Mal-Hyp, it comprises the steps:
1 gram of maltose, 4.0mL propylene glycol and 1.6mL anhydrous methanol is added in the there-necked flask with thermometer, prolong, reflux 45min under 90 DEG C of conditions, then add 0.364 gram of oxyproline again to reflux 45min, finally add 0.066 gram of strong-acid ion exchange resin and 0.802 gram of kaempferol back flow reaction 9h, after reaction terminates, obtain white crystalline target product 0.616 gram through silica gel column chromatography separation and recrystallization.Wherein, the operating process of column chromatography for separation and recrystallization is with embodiment 1.
(1) structural characterization of target product
Respectively by infrared spectra (IR), high resolution mass spectrum (HR-MS), carbon-13 nmr spectra (
13c-NMR) carry out structural characterization to embodiment gained target product Mal-Hyp, the chemical structural formula of Mal-Hyp is as follows:
。
, infrared spectra
Adopt U.S. Nicolet company's T hermo Nicolet Avatar370 type infrared spectrometric analyzer to analyze to synthesized product, the results are shown in Figure 1.As shown in Figure 1,3404.42cm
-1for-OH the stretching vibration of associated state, describe the existence of hydroxyl; 2928.57cm
-1for the stretching vibration of the carboxylic acid of hydrogen bonded, describe the existence of carboxylic acid; 1732.72cm
-1for the charateristic avsorption band of C=O.Tentatively can determine that this material and target product coincide thus.
2,
high resolution mass spectrum
Because this compound 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 2.
By to its positive ion mode map analysis, sample molecule quasi-molecular ions [M+H] can be obtained
+be 456.39271, hydrogenated molecule formula is C
17h
30nO
13, can judge that its quasi-molecule is C
17h
29nO
13, its relative molecular weight is 455.38487, and the Theoretical molecular formula of Mal-Hyp is C
17h
29nO
13, its theoretical Mr 455.38438.Therefore, sample molecule elementary composition is consistent with the elementary composition of Mal-Hyp.According to N rule, containing odd number nitrogen-atoms in molecule, coincidence theory nitrogen-atoms number.
3,
carbon-13 nmr spectra
Fig. 3 is gained compound
13c-NMR composes, 17 the spectrum peaks provided in figure represent the carbon atom that in molecule, 17 kinds of chemical environments are different, according to spectral strength judge δ by low field to the letter of High-Field carbon atom number than being 1:1:1:1:1:1:1:1:1:1:1:1:1:1:1:1:1, its digital sum is 17, consistent with carbon atom number in Mal-Hyp molecular formula.Tentatively carbon can be attributed to by figure: δ=173.429ppm is C
5 〞, δ=103.579ppm is C
1 ', δ=95.996ppm is C
2, δ=79.399ppm is C
4, δ=78.059ppm is C
5 ', δ=74.356ppm is C
2 ', δ=73.205ppm is C
3 ', δ=72.099ppm is C
4 ', δ=70.579ppm is C
3 〞, δ=70.146ppm is C
5, δ=70.085ppm is C
3, δ=64.057ppm is C
4 〞, δ=63.483ppm is C
6, δ=62.578ppm is C
6 ', δ=61.338ppm is C
1 〞, δ=57.098ppm is C
1, δ=37.761ppm is C
2 〞.From the above mentioned, this
13c-NMR spectrum is coincide with the structure of target compound Mal-Hyp.
In sum, in conjunction with infrared spectra (IR), high resolution mass spec (HR-MS) and carbon-13 nmr spectra (
13c-NMR) can determine that gained compound is Mal-Hyp.
(2) target productmal-Hyp
applied research in tobacco
1, the physics humid keeping performance test of target product
For investigating the physics humid keeping performance of target product, with blank cigarette for carrier, embodiment 2 gained target product and traditional tobacco humectant propylene glycol are carried out the research of physics humid keeping performance contrast test.First utilize the aqueous ethanolic solution of 50V% that target product Mal-Hyp and propylene glycol are mixed with the solution that massfraction is 10% respectively, then evenly spray is added in blank pipe tobacco respectively, addition is 0.3% of pipe tobacco weight, and wherein blank pipe tobacco sprays into the aqueous ethanolic solution of the 50V% of equivalent.Then by kind of the tobacco sample of 3 after application of sample at relative humidity (60 ± 2) %, temperature (22 ± 1) DEG C conditional equilibrium 48h, then respectively get 4 parts of pipe tobaccos, every part of 10g, wherein two parts are placed in relative humidity 45%, temperature 22 DEG C of fixed temperature and humidity test experiments case test environments; Other two parts are placed in relative humidity 85%, temperature 22 DEG C of fixed temperature and humidity test experiments case test environments, and every 6h weighs once, analyzes the change of instant water ratio, investigates its physics humectation effect.According to the weight differential of initial weight and the equilibrium moisture content of initial aqueous rate calculation sample pipe tobacco, test result gets 2 Duplicate Samples mean values, test continues to pipe tobacco dehydration always or water suction reaches balance, and the physics humid keeping performance effect of target product and propylene glycol sees the following form.
From above-mentioned test-results: under the drying conditions of relative humidity 45%, temperature 22 DEG C, add the equilibrium moisture content of the pipe tobacco of target product and propylene glycol all higher than blank pipe tobacco, the physics humid keeping performance wherein adding Mal-Hyp is best, is secondly propylene glycol; Under the condition of relative humidity 85%, temperature 22 DEG C, the pipe tobacco equilibrium moisture content of adding Mal-Hyp, a little more than propylene glycol, shows that compound disclosed in this invention has good humectation effect to pipe tobacco.
2, the sense organ humid keeping performance test of target product
Make solvent with 20V% aqueous ethanolic solution, embodiment 2 gained target product (Mal-Hyp) is made into the solution of massfraction 1%.Get the above-mentioned solution containing target product of 0.100g, 1.500g, 5.000g, 10.000g, 15.000g and 20.000g respectively, then evenly spray is added in the blank cigarette shreds of 100g of six 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 blank cigarette, and control sample balances 48h equally under same temperature, humidity condition.
Smoking result (see table 1) shows, the Main Function of target product to cigarette shows as and make flue gas obviously become mellow and full, soft, and comfortable taste promotes, and assorted gas and pungency reduce.When target product consumption is less, it is not clearly to cigarette effect; When its consumption is more than 1.5 ‰, occur that spine sense increases, the phenomenon that concentration reduces; When its consumption is 1.5 ‰, sucking quality is best.Therefore, best results when adding 0.15g target product Mal-Hyp in 100g cigarette, namely optimum consumption is 1.5 ‰.
The perfuming smoking result of table 1 Mal-Hyp
Claims (3)
1. a hydrophilic fragrance-enhancing tobacco humectant Mal-Hyp, its structural formula is as follows:
。
2. the preparation method of hydrophilic fragrance-enhancing tobacco humectant Mal-Hyp described in claim 1, is characterized in that, comprise the steps:
By the 16-45min that refluxes under 73-90 DEG C of condition after maltose, anhydrous methanol and dimethyl formamide or mixed with propylene glycol, then add oxyproline again to reflux 16-45min, finally add strong-acid ion exchange resin and kaempferol back flow reaction 1.5-9h, be separated and recrystallization and get final product through silica gel column chromatography after reaction terminates; Wherein, feed ratio adds 0.146-0.364 gram of oxyproline, 0.160-0.802 gram kaempferol, 0.028-0.066 gram strong-acid ion exchange resin, 1.6-2.9mL anhydrous methanol, 1.3-4.0mL dimethyl formamide or propylene glycol meter according to every 1 gram of maltose.
3. Mal-Hyp described in claim 1 is as the application of fragrance-enhancing tobacco humectant in cigarette.
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| CN106723278A (en) * | 2016-12-30 | 2017-05-31 | 常州市阿曼特化工有限公司 | A kind of preparation method of tobacco humectant |
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2014
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| US3478015A (en) * | 1966-11-14 | 1969-11-11 | Yuki Gosei Yakuhin Kogyo Kk | Process for reacting amino acid and an active carbonyl sugar in a polyhydric alcohol |
| WO2002078747A2 (en) * | 2001-03-30 | 2002-10-10 | Warner-Lambert Company Llc | Pregabalin lactose conjugates |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106723278A (en) * | 2016-12-30 | 2017-05-31 | 常州市阿曼特化工有限公司 | A kind of preparation method of tobacco humectant |
| CN106723278B (en) * | 2016-12-30 | 2017-11-24 | 重庆市木越机械制造有限公司 | A kind of preparation method of tobacco humectant |
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