CN104370986B - Sugar derivatives cigarette flavouring humectant Mal Pro, preparation method and applications - Google Patents
Sugar derivatives cigarette flavouring humectant Mal Pro, preparation method and applications Download PDFInfo
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- CN104370986B CN104370986B CN201410584038.8A CN201410584038A CN104370986B CN 104370986 B CN104370986 B CN 104370986B CN 201410584038 A CN201410584038 A CN 201410584038A CN 104370986 B CN104370986 B CN 104370986B
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- cigarette
- pro
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H7/00—Compounds containing non-saccharide radicals linked to saccharide radicals by a carbon-to-carbon bond
- C07H7/02—Acyclic radicals
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/18—Treatment of tobacco products or tobacco substitutes
- A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
- A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
- A24B15/36—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Tobacco Products (AREA)
Abstract
The invention belongs to humectant for smoke field, and in particular to a kind of sugar derivatives cigarette flavouring humectant Mal Pro, preparation method and applications.The Mal Pro structural formulas are as follows：
Description
Technical field
The invention belongs to humectant for smoke field, and in particular to a kind of sugar derivatives cigarette flavouring humectant Mal-Pro, system
Preparation Method and its application.
Background technology
Gradually attention with people to smoking and health problem, tar content in cigarette while further reducing, 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, a large amount of humectants for using mainly have propane diols, sorbierite etc. in China's cigarette, use such humectant purpose
It is to improve pipe tobacco moisture content 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 aim at a kind of sugar derivatives cigarette flavouring humectant Mal-Pro of offer, preparation method and applications.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of sugar derivatives cigarette flavouring humectant Mal-Pro, its structural formula is as follows：
。
The sugar derivatives cigarette preparation method of flavouring humectant Mal-Pro, it comprises the following steps：
After by maltose, absolute methanol and dimethylformamide or mixed with propylene glycol, flowed back under the conditions of 73-89 DEG C
10-40min, is subsequently adding proline and flows back again 10-40min, is eventually adding strong-acid ion exchange resin and myricetin
Back flow reaction 2-8h；After reaction terminates, separated through silica gel column chromatography and recrystallization is obtained final product；Wherein, rate of charge is according to every 1 gram of wheat
0.128-0.320 grams of proline of bud sugar addition, 0.018-0.088 grams of myricetin, 0.02-0.05 grams of strong acidic ion are exchanged
Resin, 1.0-1.5mL absolute methanols, 0.7-1.5mL dimethylformamides or propane diols meter.
Specifically, eluent used by column chromatography for separation is the mixed liquor of n-butanol, glacial acetic acid and water composition, the volume of three
Than being 4：2：1, developer is ethanol solution of ninhydrin.
Applications of the Mal-Pro as fragrance-enhancing tobacco humectant in cigarette.
The synthetic route of present invention design is as follows：
。
Used as a kind of latent aroma compounds, its pyrolysis product is generally the heterocycles such as furanone, pyrazine to the compounds of this invention Mal-Pro
Compound, the fragrant and sweet of tobacco can be increased and baking is fragrant, itself contain a large amount of hydrophilic radicals, it is current as tobacco humectant
It is still rare.
Compared to the prior art, beneficial effects of the present invention：
1st, it is of the invention first with maltose as initiation material, with solid acid as catalyst, with myricetin as inhibitor, with dried meat
Propylhomoserin react, successfully synthesize a kind of Maillard reaction intermediate-Mal-Pro, study and determine synthesis technology condition and
Preferred plan.The method process is simple, raw material are easy to get, yield is higher, are adapted to industrialized production.
2nd, the present invention develops a kind of novel hydrophilic type tobacco humectant, is applied to Mal-Pro as humectant first
In cigarette, tested by physics humid keeping performance and inherent sensory quality assessment, it is found that it has good physics humectation to cigarette
Effect, and cigarette excitant and miscellaneous gas 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-Pro is rarely reported, route tool
Have the advantages that raw material is easy to get, easy to operate, yield is significantly improved.Target product of the invention is imitated due to the effect to tobacco product
Fruit is obvious, therefore the bright prospects with significant industrial application value and popularization and application.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of target product Mal-Pro；
Fig. 2 is the high resolution mass spectrum figure of target product Mal-Pro；
Fig. 3 is the carbon-13 nmr spectra figure of target product Mal-Pro.
Specific 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 below portion of reagent used and instrument in embodiment.
Maltose, proline（99%, Aladdin chemical reagents corporation）；Myricetin（HPLC grades, French Extrasynthese
Company）；Absolute methanol, absolute ethyl alcohol, dimethylformamide, n-butanol, glacial acetic acid（AR, the triumphant logical chemical reagent in Tianjin is limited
Company）；Amberlite IR-120 (H) ion exchange resin（Alfa Aesar）；Silica gel（Chemistry is pure, and Qingdao Haiyang chemical industry has
Limit 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 pump（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 sugar derivatives cigarette preparation method of flavouring humectant Mal-Pro, it comprises the following steps：
1 gram of maltose, 0.7mL dimethylformamides, 1.5mL are added in thermometer, the there-necked flask of condenser pipe
Absolute methanol, flow back 10min under the conditions of 73 DEG C, is subsequently adding 0.128 gram of proline and flows back again 10min, is eventually adding
0.02 gram of strong-acid ion exchange resin and 0.018 gram of myricetin back flow reaction 2h.Reaction terminate after through silica gel column chromatography separate,
It is recrystallized to give 0.457 gram of white crystalline target product.Wherein, eluent used by column chromatography for separation is n-butanol, glacial acetic acid
The mixed liquor constituted with water, the volume ratio of three is 4：2：1, developer is ethanol solution of ninhydrin；Recrystallizing solvent for use is
Volume ratio is 1:1 absolute ethyl alcohol and the mixed solution of absolute methanol.
Embodiment 2
A kind of sugar derivatives cigarette preparation method of flavouring humectant Mal-Pro, it comprises the following steps：
1 gram of maltose, 1.0mL dimethylformamides, 1.5mL are added in thermometer, the there-necked flask of condenser pipe
Absolute methanol, flow back 20min under the conditions of 80 DEG C, is subsequently adding 0.32 gram of proline and flows back again 20min, is eventually adding 0.03
Gram strong-acid ion exchange resin and 0.068 gram of myricetin back flow reaction 4h.Reaction is separated through silica gel column chromatography after terminating, tied again
Crystalline substance obtains 0.857 gram of white crystalline target product.Wherein, the operating process of column chromatography for separation and recrystallization is with embodiment 1.
Embodiment 3
A kind of sugar derivatives cigarette preparation method of flavouring humectant Mal-Pro, it comprises the following steps：
1 gram of maltose, 1.5mL propane diols and 1.0mL are added in thermometer, the there-necked flask of condenser pipe without water beetle
Alcohol, flow back 40min under the conditions of 89 DEG C, is subsequently adding 0.25 gram of proline and flows back again 20min, is eventually adding 0.05 gram of strong acid
Property ion exchange resin and 0.088 gram of myricetin backflow 8h reactions.Reaction is separated through silica gel column chromatography after terminating, is recrystallized to give
0.632 gram of white crystalline target product.Wherein, the operating process of column chromatography for separation and recrystallization is with embodiment 1.
（One）The structural characterization of target product
By infrared spectrum（IR）, high resolution mass spectrum（HR-MS）, carbon-13 nmr spectra（13C-NMR）Respectively to embodiment institute
Obtaining target product Mal-Pro carries out structural characterization, and the chemical structural formula of Mal-Pro 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 shown in the drawing, 3500.12cm-1And 3195.99cm-1It is the carboxylic acid of Hydrogenbond
Stretching vibration, illustrates the presence of carboxylic acid；2987.86cm-1And 2938.22cm-1It is saturated hydrocarbyl C-H stretching vibrations,
1760.73cm-1It is the characteristic absorption peak of C=O, 1256.54cm-1, 1215.85cm-1, 1139.76cm-1And 1020.61cm-1For
C-O-C key chatterings are coupled.Thus can primarily determine that the material coincide with target product.
2nd, high resolution mass spectrum
It is because the compound Polarity comparision is strong and 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+It is 440.39278, hydrogenation
Molecular formula is C17H30NO12, can determine whether that its quasi-molecule is C17H29NO12, its relative molecular weight is 439.38494, and Mal-Pro
Theoretical molecular formula is C17H29NO12, its theoretical Mr 439.38535, therefore, sample molecule elemental constituent and Mal-Pro
Elemental constituent it is consistent.According to N rules, odd number nitrogen-atoms is contained in molecule, meet theoretical nitrogen-atoms number.
3rd, carbon-13 nmr spectra
Fig. 3 is gained compound13C-NMR is composed, and 17 spectral peaks be given in figure represent 17 kinds of chemical environments in molecule
Different carbon atoms, judges that δ is 1 by low field to High-Field carbon atom number letter ratio according to spectral strength: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-Pro molecular formula.Can tentatively by carbon by figure
It is attributed to：δ=176.243ppm is C5〞, δ=107.731ppm is C1′, δ=93.918ppm is C2, δ=79.525ppm is C4, δ=
78.281ppm is C5′, δ=76.051ppm is C2′, δ=72.924ppm is C3′, δ=71.165ppm is C4′, δ=69.287ppm is
C5, δ=69.076ppm is C3, δ=68.766ppm is C1〞, δ=65.197ppm is C6, δ=62.937ppm is C6′, δ=
58.342ppm is C1, δ=57.187ppm is C4〞, δ=28.712ppm is C2〞, δ=23.152ppm is C3〞.From the above mentioned, this13C-
H NMR spectroscopy coincide with the structure of object Mal- Pro.
In sum, 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-Pro.
（Two）Application study of the target product in tobacco
1st, the physics humid keeping performance test of target product
Be the physics humid keeping performance for investigating target product, with 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 the ethanol water of 50V% by mesh
Mark product Mal-Pro 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 pipe tobacco sprays into the ethanol water of the 50V% of equivalent.Then 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
In 22 DEG C of closed containers of degree, 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 and puts 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.
Result of the test understands, under relative humidity 45%, the drying condition of 22 DEG C of temperature, adds target product and propane diols
The equilibrium moisture content of pipe tobacco be above blank pipe tobacco, wherein the physics humid keeping performance of addition Mal-Pro is preferably, next to that the third two
Alcohol；And under conditions of relative humidity 85%, 22 DEG C of temperature, the pipe tobacco equilibrium moisture content for adding Mal-Pro 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, the target product Mal-Pro of embodiment 2 is made into the solution of mass fraction 1%.
1.00g, 5.00g, 10.00g, 15.00g, 20.00g and the 25.00 above-mentioned solution containing target product are taken respectively, then uniform spray
It is added in six parts of 100g blank cigarette shreds of non-flavoring and casing, rolls, respectively pick out 100 same weight cigarette, is placed in temperature
22 DEG C ± 1 DEG C of degree, 48h is balanced in the climatic chamber of humidity 60% ± 2%, is smoked panel test.Control sample is blank cigarette, and control sample is same
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 ‰, there is spine sense increase, the phenomenon of concentration reduction；The sucking quality when its consumption is 2 ‰
It is best.Therefore, best results, i.e. optimum consumption are 2 ‰ when 0.2g target products are added in 100g cigarette.
The perfuming smoking result of the Mal-Pro of table 1
Claims (1)
1. application of the sugar derivatives cigarette with flavouring humectant Mal-Pro as fragrance-enhancing tobacco humectant in cigarette, its feature exists
In sugar derivatives cigarette is as follows with flavouring humectant Mal-Pro structural formulas：
；
The sugar derivatives cigarette preparation method of flavouring humectant Mal-Pro, it comprises the following steps：
After by maltose, absolute methanol and dimethylformamide or mixed with propylene glycol, flow back 10- under the conditions of 73-89 DEG C
40min, is subsequently adding proline and flows back again 10-40min, is eventually adding strong-acid ion exchange resin and myricetin backflow
Reaction 2-8h；After reaction terminates, separated through silica gel column chromatography and recrystallization is obtained final product；Wherein, rate of charge is according to every 1 gram of maltose
0.128-0.320 grams of proline of addition, 0.018-0.088 grams of myricetin, 0.02-0.05 grams of strong-acid ion exchange resin,
1.0-1.5mL absolute methanols, 0.7-1.5mL dimethylformamides or propane diols meter.
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| CN201410584038.8A CN104370986B (en) | 2014-10-28 | 2014-10-28 | Sugar derivatives cigarette flavouring humectant Mal Pro, preparation method and applications |
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| CN105105324B (en) * | 2015-08-04 | 2016-09-14 | 川渝中烟工业有限责任公司 | Tobacco humectant and its preparation method and application |
| CN105661630B (en) * | 2016-01-07 | 2017-03-22 | 安徽中烟工业有限责任公司 | Application of sophorolipid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101397313A (en) * | 2007-09-27 | 2009-04-01 | 武汉烟草(集团)有限公司 | Maillard reaction intermediate, preparation method and use thereof |
-
2014
- 2014-10-28 CN CN201410584038.8A patent/CN104370986B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101397313A (en) * | 2007-09-27 | 2009-04-01 | 武汉烟草(集团)有限公司 | Maillard reaction intermediate, preparation method and use thereof |
Non-Patent Citations (3)
| Title |
|---|
| "Isolation and purification of Amadori compounds by semi-preparative reversed-phase high-performance liquid chromatography";N. MOLL，等;《Journal of Chromatography》;19811231;第206卷;第186-192页 * |
| "On the Influence of the Carbohydrate Moiety on Chromophore Formation during Food-Related Maillard Reactions of Pentoses，Hexoses，and Disaccharides";Oliver Frank，等;《Helvetica Chimica Acta》;20001231;第83卷;第3246-3261页 * |
| "Recent procedures in the isolation and purification of Amadori compounds -applications";Nicole Moll，等;《Instrumental Analysis of Foods》;19831231;第1卷;第279-301页 * |
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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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