CN104341463B - Cigarette monomer perfume Mal Ile, preparation method and applications - Google Patents
Cigarette monomer perfume Mal Ile, preparation method and applications Download PDFInfo
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- CN104341463B CN104341463B CN201410586132.7A CN201410586132A CN104341463B CN 104341463 B CN104341463 B CN 104341463B CN 201410586132 A CN201410586132 A CN 201410586132A CN 104341463 B CN104341463 B CN 104341463B
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Abstract
The present invention relates to a kind of Novel tobacco monomer perfume Mal Ile, preparation method and applications.The Mal Ile structural formulas are as follows：
Description
Technical field
The invention belongs to essence and flavoring agent and tobacco manufacture field, and in particular to a kind of Novel tobacco monomer perfume Mal-Ile,
Preparation method and applications.
Background technology
As people are to smoking and the gradually attention of health problem, tar content in cigarette is while further reduction, cigarette
Comfortableness is deteriorated, and embodies a concentrated reflection of moisture in cut tobacco and scatters and disappears that fast, main flume moisture is relatively low, excitant is bigger than normal, oral cavity is dry and phlegm
It is many etc..At present, the humectant largely used in China's cigarette mainly has propane diols, sorbierite etc., uses such humectant purpose
It is to improve the moisture content of pipe tobacco in process, improves pipe tobacco degrading resistance property, but above-mentioned humectant is to cigarette rags
The maintenance of moisture content and the improvement of sensory comfort are unsatisfactory.
The content of the invention
Present invention aims at provide a kind of Novel tobacco monomer perfume Mal-Ile, preparation method and applications.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of cigarette monomer perfume Mal-Ile, its structural formula is as follows：
。
Cigarette monomer perfume Mal-Ile preparation method, it comprises the following steps：
After maltose, absolute methanol and dimethylformamide or mixed with propylene glycol, flowed back under the conditions of 76-89 DEG C
20-45min, then adds isoleucine and flows back again 20-45min, be eventually adding strong-acid ion exchange resin and kaempferia galamga
Phenol back flow reaction 2-8h；After reaction terminates, produced through silica gel column chromatography separation and recrystallization；Wherein, rate of charge is according to every 1 gram
Maltose add 0.138-0.396 grams of isoleucine, 0.249-1.245 grams of Kaempferol, 0.035-0.068 grams of highly acid from
Sub-exchange resin, 1.7-2.8mL absolute methanols, 1.5-3.9mL dimethylformamides or propane diols meter.
Specifically, eluent used in column chromatography for separation is the mixed liquor of n-butanol, glacial acetic acid and water composition, the volume of three
Than for 6：1：1, developer is ethanol solution of ninhydrin.
Applications of the Mal-Ile as fragrance-enhancing tobacco humectant in cigarette.
The synthetic route that the present invention is designed is as follows：
。
The compounds of this invention Mal-Ile is its property stabilization under a kind of latent aroma compounds, normal temperature, is white tasteless crystal thing
Matter, but it produces material such as furanone, ketene that tool is significantly increased the fragrant and sweet of tobacco and baking perfume by heating cleavable
Compound, in addition, itself contain a large amount of hydrophilic radicals, it is still rare at present using the compound as fragrance-enhancing tobacco humectant.
Compared to the prior art, beneficial effects of the present invention：
1st, the present invention is first using maltose as initiation material, using solid acid as catalyst, using Kaempferol as inhibitor, and different
Leucine reacts, and successfully synthesizes a kind of latent Studies of The Aromatic Substances-Mal-Ile, studies and determines synthesis technology condition and optimal side
Case.This method technique is simple, raw material is easy to get, yield is higher, is adapted to industrialized production.
2nd, the present invention develops a kind of Novel tobacco monomer perfume, first should using Mal-Ile as fragrance-enhancing tobacco humectant
For in cigarette, by, in sensory quality assessment, as a result showing that it has to pipe tobacco in the test of cigarette physics humid keeping performance and cigarette
There is excellent physics humectation effect, and the excitant and miscellaneous gas of cigarette can be reduced, improve the mellow and full sense of cigarette smoke and comfortableness.
3rd, advantages of the present invention：According to existing document analysis, the synthesis about Mal-Ile is rarely reported, route tool
Have the advantages that raw material is easy to get, easy to operate, yield is significantly improved.The target product of the present invention is due to the effect effect to tobacco product
Fruit substantially, therefore has the bright prospects of significant industrial application value and popularization and application.
Brief description of the drawings
Fig. 1 is target product Mal-Ile infrared spectrogram；
Fig. 2 is target product Mal-Ile high resolution mass spectrum figure；
Fig. 3 is target product Mal-Ile carbon-13 nmr spectra figure.
Embodiment
Below by way of specific embodiment, the present invention is described in detail, but protection scope of the present invention not limited to this.
It is portion of reagent and instrument used in embodiment below.
Maltose, isoleucine（99%, Aladdin chemical reagents corporation）；Kaempferol（HPLC grades, France
Extrasynthese companies）；Absolute methanol, absolute ethyl alcohol, dimethylformamide, propane diols, n-butanol, glacial acetic acid（AR, day
Kai Tong chemical reagent Co., Ltd of Jinshi City）；Amberlite IR-120 (H) ion exchange resin（Alfa Aesar）；Silica gel（Change
Learn pure, Qingdao Marine Chemical Co., Ltd.）.
Thermo Nicolet Avatar370 infrared spectrometers（Nicolet companies of the U.S.）；Bruker Avance
AMX-400 nuclear magnetic resonance spectrometers（Bruker companies of the U.S.）；BS200SWE1 type electronic balances（Sensibility reciprocal：0.0001g, Beijing match is more
Liz balance Co., Ltd）；R-215 type Rotary Evaporators（BUCHI companies of Switzerland）；V-700 vavuum pumps（Switzerland BUCHI is public
Department）；DLSB -20/60 DEG C of sub-cooled circulating pumps（The U.S. strong experimental instruments and equipment limited in Shanghai）；KDM type regulating temperature electrothermal covers（Mountain
Dong Hualu electric heating Instrument Ltd.）.
Embodiment 1
A kind of cigarette monomer perfume Mal-Ile preparation method, it comprises the following steps：
1 gram of maltose, 1.5mL dimethylformamides, 2.8mL are added in thermometer, the three-necked flask of condenser pipe
Absolute methanol, flow back 20min under the conditions of 76 DEG C, then adds 0.138 gram of isoleucine and flows back again 20min, is eventually adding
0.035 gram of strong-acid ion exchange resin and 0.249 gram of Kaempferol back flow reaction 2.0h；After reaction terminates, through silica gel column chromatography
Separate, be recrystallized to give 0.395 gram of white crystalline target product.Wherein, eluent used in column chromatography for separation is n-butanol, ice
The mixed liquor of acetic acid and water composition, the volume ratio of three is 6：1：1, developer is ethanol solution of ninhydrin；Recrystallization is used molten
Agent is that volume ratio is 1:1 absolute ethyl alcohol and the mixed solution of absolute methanol.
Embodiment 2
A kind of cigarette monomer perfume Mal-Ile preparation method, it comprises the following steps：
1 gram of maltose, 3.6mL dimethylformamides, 2.0mL are added in thermometer, the three-necked flask of condenser pipe
Absolute methanol, flow back 35min under the conditions of 85 DEG C, then adds 0.256 gram of isoleucine and flows back again 35min, is eventually adding
0.053 gram of strong-acid ion exchange resin and 1.019 grams of h of Kaempferol back flow reaction 6.0；After reaction terminates, through silica gel column chromatography
Separate, be recrystallized to give 0.845 gram of white crystalline target product.Wherein, the operating process of column chromatography for separation and recrystallization is same
Embodiment 1.
Embodiment 3
A kind of cigarette monomer perfume Mal-Ile preparation method, it comprises the following steps：
1 gram of maltose, 3.9mL propane diols and 1.7mL are added in thermometer, the three-necked flask of condenser pipe without water beetle
Alcohol, flow back 45min under the conditions of 89 DEG C, then adds 0.396 gram of isoleucine and flows back again 45min, is eventually adding 0.068 gram
Strong-acid ion exchange resin and 1.245 grams of Kaempferol back flow reaction 8.0h；After reaction terminates, separated through silica gel column chromatography, again
Crystallization obtains 0.584 gram of white crystalline target product.Wherein, column chromatography for separation and the operating process be the same as Example 1 of recrystallization.
（One）The structural characterization of target product
Pass through infrared spectrum（IR）, high resolution mass spectrum（HR-MS）, carbon-13 nmr spectra（13C-NMR）Respectively to embodiment institute
Obtain target product Mal-Ile and carry out structural characterization, Mal-Ile chemical structural formula is as follows：
。
1st, infrared spectrum
To synthesized product using U.S. Nicolet company's T hermo Nicolet Avatar370 types infrared spectrum point
Analyzer is analyzed, and as a result sees Fig. 1.As seen from the figure, 3392.01cm-1For the hydroxyl stretching vibration of associated state, hydroxyl is illustrated
Presence, 1732.45cm-1For carbonyl characteristic absorption peak.Thus it can primarily determine that the material coincide with target product.
2nd, high resolution mass spectrum
Because the compound Polarity comparision is strong, and it is more sensitive to heat, therefore use electric spray ion source（ESI）High-resolution
Rate mass spectrum（HR-MS）Carry out mass spectral analysis（High resolution mass spectrometer Exactive Orbitrap, Thermo companies of the U.S.）.It is molten
Agent is mobile phase from 50% methanol aqueous solution, as a result sees Fig. 2.
By the way that to its positive ion mode map analysis, sample molecule quasi-molecular ions [M+H] can be obtained+For 456.43464, hydrogenation
Molecular formula is C18H34NO12, can determine whether its quasi-molecule is C18H33NO12, its relative molecular weight is 455.42680, and Mal-Ile
Theoretical molecular formula is C18H33NO12, its theoretical Mr 455.42631, therefore, sample molecule elemental constituent and Mal-Ile
Elemental constituent it is consistent.According to N rules, contain odd number nitrogen-atoms in molecule, meet theoretical nitrogen-atoms number.
3rd, carbon-13 nmr spectra
Fig. 3 is gained compound13C-NMR is composed, and 18 spectral peaks provided in figure represent 18 kinds of chemical environments in molecule
Different carbon atoms, according to spectral strength judge δ by low field to the simple ratio of High-Field carbon atom number for 1:1:1:1:1:1:1:1:1:
1:1:1:1:1:1:1:1:1, its digital sum is 18, consistent with carbon atom number in Mal-Ile molecular formula.By figure can tentatively by
Carbon is attributed to：δ=172.680ppm is C6〞, δ=108.951ppm is C1′, δ=96.152ppm is C2, δ=77.361ppm is C4, δ=
77.043ppm for C5′, δ=76.725ppm is C2′, δ=71.067ppm is C3′, δ=70.780ppm is C4′, δ=70.565ppm is
C5, δ=70.327ppm is C3, δ=68.659ppm is C6, δ=66.374ppm is C6′, δ=61.089ppm is C1〞, δ=
59.783ppm for C1, δ=37.986ppm is C2〞, δ=24.881ppm is C3〞, δ=15.833ppm is C5〞, δ=11.450ppm is
C4〞.From the above mentioned, this13C-NMR is composed and object Mal-Ile structure is coincide.
In summary, with reference to infrared spectrum（IR）, high resolution mass spec (HR-MS) and carbon-13 nmr spectra（13C-NMR）Can
It is determined that gained compound is Mal-Ile.
（Two）Application study of the target product in tobacco
1st, the physics humid keeping performance test of target product
To investigate the physics humid keeping performance of target product, using blank cigarette as carrier, by the gained target product of embodiment 2 and
Traditional tobacco humectant propane diols carries out the research of physics humid keeping performance contrast test, first with 50V% ethanol water by mesh
Mark product Mal-Ile and propane diols are configured to the solution that mass fraction is 10% respectively, and then uniform spray is added to blank pipe tobacco respectively
In, addition is the 0.3% of pipe tobacco weight, and wherein blank control pipe tobacco sprays into the 50V% of equivalent ethanol water.Then it will add
3 kinds of tobacco sample after sample are in relative humidity（60±2）%, temperature（22±1）DEG C conditional equilibrium 48h, then respectively takes 4 parts of pipe tobaccos,
Every part of 10g, wherein two parts are placed in relative humidity 45%, 22 DEG C of constant temperature and humidity test experiments case test environments of temperature, two parts in addition
It is placed in relative humidity 85%, 22 DEG C of constant temperature and humidity test experiments case test environments of temperature, is weighed once per 6h, to immediately aqueous
The change of rate is analyzed, and investigates its physics humectation effect, is calculated according to the weight differential with initial weight and initial aqueous rate
The equilibrium moisture content of sample pipe tobacco, test result takes 2 Duplicate Samples average values, and test is continued for pipe tobacco dehydration or water suction reaching
To balance, the physics humid keeping performance effect of target product and propane diols see the table below.
Results showed that is under relative humidity 45%, the drying condition of 22 DEG C of temperature, addition target product and propane diols
The equilibrium moisture content of pipe tobacco be above blank pipe tobacco, wherein addition Mal-Ile physics humid keeping performance is preferably, next to that the third two
Alcohol；And under conditions of relative humidity 85%, 22 DEG C of temperature, addition Mal-Ile pipe tobacco equilibrium moisture content is slightly above propane diols,
Show that there is compound disclosed in this invention preferable humectation to act on to pipe tobacco.
2nd, the sense organ humid keeping performance test of target product
Solvent is made with 20V% ethanol waters, by the gained target product of embodiment 2（Mal-Ile）It is made into mass fraction 1%
Solution.The above-mentioned solution containing target product of 1.00g, 2.00g, 5.00g, 10.00g, 17.50g and 20.00g, Ran Houjun are taken respectively
Even spray is added in the 100g blank cigarette shreds of six parts of non-flavoring and casings, is rolled, is respectively picked out 100 same weight cigarette, put
In 22 DEG C ± 1 DEG C of temperature, 48h is balanced in the climatic chamber of humidity 60% ± 2%, is smoked panel test.Control sample is blank cigarette, control sample
Equally 48h is balanced under the conditions of identical epidemic disaster.
Smoking result（It is shown in Table 1）Show, target product the main function of cigarette is shown as making flue gas substantially become it is mellow and full,
Soft, comfortable taste lifting, miscellaneous gas and excitant are reduced.When target product consumption is smaller, it is not very to cigarette effect
Substantially；When its consumption is more than 1.75 ‰, there is spine sense increase, the phenomenon of concentration reduction；Inhaled when its consumption is 1.75 ‰
Food matter is best.Therefore, best results when 0.175g target products are added in 100g cigarette, i.e. optimum consumption is
1.75‰。
The Mal-Ile of table 1 perfuming smoking result
Claims (2)
1. a kind of cigarette monomer perfume Mal-Ile preparation method, it is characterised in that the cigarette with monomer perfume Mal-Ile its
Structural formula is as follows：
；
Specifically include following steps：
After maltose, absolute methanol and dimethylformamide or mixed with propylene glycol, flow back 20- under the conditions of 76-89 DEG C
45min, then adds isoleucine and flows back again 20-45min, is eventually adding strong-acid ion exchange resin and Kaempferol is returned
Stream reaction 2-8h；After reaction terminates, produced through silica gel column chromatography separation and recrystallization；Wherein, rate of charge is according to every 1 gram of malt
0.138-0.396 grams of isoleucine of sugar addition, 0.249-1.245 grams of Kaempferol, 0.035-0.068 grams of strong acidic ion are handed over
Change resin, 1.7-2.8mL absolute methanols, 1.5-3.9mL dimethylformamides or propane diols meter.
2. the cigarette prepared using preparation method described in claim 1 is with monomer perfume Mal-Ile as fragrance-enhancing tobacco humectation
Application of the agent in cigarette.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103349356A (en) * | 2013-06-19 | 2013-10-16 | 河南中烟工业有限责任公司 | Cigarette aroma enhancement humectant 1-L-leucine-1-deoxidation-D-fructose and preparation method thereof |
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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 |
| CN101704850A (en) * | 2009-10-21 | 2010-05-12 | 安徽中烟工业公司 | Method for separating and extracting compound of Amadori of Maillard reaction midbody |
| RU2014131057A (en) * | 2011-12-27 | 2016-02-20 | Морисита Дзинтан Ко., Лтд. | MAYLARD REACTION INHIBITOR |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103349356A (en) * | 2013-06-19 | 2013-10-16 | 河南中烟工业有限责任公司 | Cigarette aroma enhancement humectant 1-L-leucine-1-deoxidation-D-fructose and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| Studies on structures and activities of initial Maillard reaction products byelectrospray ionisation mass spectrometry combined with liquid chromatographyin processing of red ginseng;Qin-Qin Du et al.;《Food Chemistry》;20120508;第135卷;832-838 * |
| 黄酮醇抑制丙烯酰胺在美拉德反应中的形成及与抗氧化间的相关性;程军等;《浙江大学学报（农业与生命科学版）》;20130315;第39卷(第2期);178-184 * |
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