CN104341466B - Cigarette monomer perfume Mal Val, preparation method and applications - Google Patents
Cigarette monomer perfume Mal Val, preparation method and applications Download PDFInfo
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- CN104341466B CN104341466B CN201410586186.3A CN201410586186A CN104341466B CN 104341466 B CN104341466 B CN 104341466B CN 201410586186 A CN201410586186 A CN 201410586186A CN 104341466 B CN104341466 B CN 104341466B
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Abstract
The present invention relates to a kind of Novel tobacco monomer perfume Mal Val, preparation method and applications.The Mal Val structures 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-Val, system
Preparation Method and its application.
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-Val, 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-Val, its structural formula is as follows：
。
Cigarette monomer perfume Mal-Val preparation method, it comprises the following steps：
After maltose, absolute methanol, dimethylformamide or propane diols, flow back 20- under the conditions of 73-88 DEG C
40min, then adds valine and flows back again 20-40min, be eventually adding strong-acid ion exchange resin and Quercetin backflow
React 1-7h；After reaction terminates, produced through silica gel column chromatography separation and recrystallization；Wherein, rate of charge is according to every 1 gram of maltose
0.130-0.325 grams of valine of addition, 0.168-0.838 grams of Quercetin, 0.035-0.067 grams of strong acidic ion exchange tree
Fat, 1.8-3.3mL absolute methanols, 1.3-3.6mL 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 4：1：1, developer is ethanol solution of ninhydrin.
Applications of the Mal-Val 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-Val 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 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 Quercetin as inhibitor, with figured silk fabrics
Propylhomoserin react, successfully synthesize a kind of Maillard reaction intermediate-Mal-Val, study and determine synthesis technology condition and
Preferred plan.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 hydrophilic type compound, first should using Mal-Val as fragrance-enhancing tobacco humectant
For in cigarette, by the test of physics humid keeping performance and inherent sensory quality assessment, it is found that it has good physics to cigarette
Humectation is acted on, and can reduce cigarette excitant and miscellaneous gas, improves 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-Val 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-Val infrared spectrogram；
Fig. 2 is target product Mal-Val high resolution mass spectrum figure；
Fig. 3 is target product Mal-Val 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, valine（99%, Aladdin chemical reagents corporation）；Quercetin（HPLC grades, Sigma Co., USA）；Nothing
Water methanol, absolute ethyl alcohol, dimethylformamide, propane diols, n-butanol, glacial acetic acid（AR, the triumphant logical limited public affairs of chemical reagent in Tianjin
Department）；Amberlite IR-120 (H) ion exchange resin（Alfa Aesar）；Silica gel（Chemistry is pure, and Qingdao Haiyang chemical industry is limited
Company）.
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-Va preparation method, it comprises the following steps：
1 gram of maltose, 1.3mL dimethylformamides, 3.3mL are added in thermometer, the three-necked flask of condenser pipe
Absolute methanol, flow back 20min under the conditions of 73 DEG C, then adds 0.130 gram of valine and flows back again 20min, is eventually adding
0.035 gram of strong-acid ion exchange resin and 0.168 gram of Quercetin back flow reaction 1h；After reaction terminates, through silica gel column chromatography point
From, be recrystallized to give 0.371 gram of white crystalline target product.Wherein, eluent used in column chromatography for separation is n-butanol, ice second
The mixed liquor that acid and water are constituted, the volume ratio of three is 4：1：1, developer is ethanol solution of ninhydrin；Recrystallize solvent for use
It is 1 for volume ratio:1 absolute ethyl alcohol and the mixed solution of absolute methanol.
Embodiment 2
A kind of cigarette monomer perfume Mal-Va preparation method, it comprises the following steps：
1 gram of maltose, 3.2mL dimethylformamides, 2.0mL are added in thermometer, the three-necked flask of condenser pipe
Absolute methanol, flow back 28min under the conditions of 81 DEG C, then adds 0.286 gram of valine and flows back again 28min, is eventually adding
0.05 gram of strong-acid ion exchange resin and 0.662 gram of h of Quercetin back flow reaction 4；After reaction terminates, through silica gel column chromatography point
From, be recrystallized to give 0.848 gram of white crystalline target product.Wherein, the operating process of column chromatography for separation and recrystallization is with real
Apply example 1.
Embodiment 3
A kind of cigarette monomer perfume Mal-Va preparation method, it comprises the following steps：
1 gram of maltose, 3.6mL propane diols and 1.8mL are added in thermometer, the three-necked flask of condenser pipe without water beetle
Alcohol, flow back 40min under the conditions of 88 DEG C, then adds 0.325 gram of valine and flows back again 40min, is eventually adding 0.067 gram strong
Acid-exchange resin and 0.838 gram of Quercetin back flow reaction 7h；After reaction terminates, separate, recrystallize through silica gel column chromatography
Obtain 0.597 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-Val and carry out structural characterization, Mal-Val chemical structural formula is as follows：
。
, 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. 1.3396.62cm-1For the O-H stretching vibrations of associated state, the presence of hydroxyl is illustrated；
2934.98cm-1For the stretching vibration of the carboxylic acid of Hydrogenbond, illustrate the presence of carboxylic acid；1731.92cm-1Inhaled for C=O feature
Receive peak, 1239.92cm-1, 1128.12cm-1And 1071.47cm-1It is coupled for C-O-C key chatterings.Thus the material can be primarily determined that
It is 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 442.40926, hydrogenation
Molecular formula is C17H32NO12, can determine whether its quasi-molecule is C17H31NO12, its relative molecular weight is 441.40142, and Mal-Val
Theoretical molecular formula is C17H31NO12, its theoretical Mr 441.40103, therefore, sample molecule elemental constituent and Mal-Val
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 17 spectral peaks provided in figure represent 17 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, its digital sum is 17, consistent with carbon atom number in Mal-Ser molecular formula.Can be tentatively by carbon by figure
It is attributed to：δ=169.510ppm is C2〞, δ=108.468ppm is C1′, δ=96.192ppm is C2, δ=77.469ppm is C4, δ=
77.150ppm for C5′, δ=76.830ppm is C2′, δ=71.006ppm is C3′, δ=70.525ppm is C4′, δ=70.366ppm is
C5, δ=70.214ppm is C3, δ=63.643ppm is C1〞, δ=62.851ppm is C6, δ=61.306ppm is C6′, δ=
54.285ppm for C1, δ=27.992ppm is C3〞, δ=16.235ppm is C5〞, δ=15.949ppm is C4〞.From the above mentioned, this13C-
The structure of H NMR spectroscopy and object Mal-Val 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-Val.
（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-Val 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 closed containers of temperature, two parts are placed in relative humidity 85%, temperature in addition
Spend in 22 DEG C of closed containers, weighed once per 12h, the change to instant moisture content is analyzed, and investigates its physics humectation effect,
The equilibrium moisture content of sample pipe tobacco is calculated according to the weight differential with initial weight and initial aqueous rate, test result takes 2 to put down
Row sample average value, test is continued for reaching balance, the physics humectation of target product and propane diols to pipe tobacco dehydration or water suction
Energy effect 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-Val 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-Val 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 target product of embodiment 2（Mal-Val）It is made into the molten of mass fraction 1%
Liquid.The above-mentioned solution containing target product of 0.1g, 5.0g, 10.0g, 15.0g, 20.0g and 25.0g is taken respectively, and then uniform spray adds
Into the 100g blank cigarette shreds 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, 48h is balanced in the climatic chamber of humidity 60% ± 2%, is smoked panel test.Control sample is blank cigarette, and control sample equally exists
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 2.0 ‰, there is spine sense increase, the phenomenon of concentration reduction；Sucked when its consumption is 2.0 ‰
Quality is best.Therefore, best results, i.e. optimum consumption are 2.0 ‰ when 0.2g target products are added in 100g cigarette.
The Mal-Val of table 1 perfuming smoking result
Claims (2)
1. a kind of cigarette monomer perfume Mal-Val preparation method, it is characterised in that cigarette monomer perfume Mal-Val knot
Structure formula is as follows：
；
Specifically include following steps：
After maltose, absolute methanol, dimethylformamide or propane diols, flow back 20-40min under the conditions of 73-88 DEG C, so
Valine is added afterwards to flow back again 20-40min, is eventually adding strong-acid ion exchange resin and Quercetin back flow reaction 1-
7h；After reaction terminates, produced through silica gel column chromatography separation and recrystallization；Wherein, rate of charge is added according to every 1 gram of maltose
0.130-0.325 grams of valine, 0.168-0.838 grams of Quercetin, 0.035-0.067 grams of strong-acid ion exchange resin,
1.8-3.3mL absolute methanols, 1.3-3.6mL dimethylformamides or propane diols meter.
2. the cigarette prepared using preparation method described in claim 1 is with monomer perfume Mal-Val 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 |
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| 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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Address after: 450000 Yulin South Road, Henan, Zheng Dong, No. 16 South Road, Zhengzhou Applicant after: China Tobacco Henan Industrial Co., Ltd. Address before: 450000 Zhengzhou agricultural road, Henan, No. 29 Applicant before: China Tobacco Henan Industrial Co., Ltd. |
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