CN104341466A - Monomer flavor Mal-Val used for cigarettes as well as preparation method and application thereof - Google Patents
Monomer flavor Mal-Val used for cigarettes as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN104341466A CN104341466A CN201410586186.3A CN201410586186A CN104341466A CN 104341466 A CN104341466 A CN 104341466A CN 201410586186 A CN201410586186 A CN 201410586186A CN 104341466 A CN104341466 A CN 104341466A
- Authority
- CN
- China
- Prior art keywords
- mal
- val
- gram
- cigarette
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Manufacture Of Tobacco Products (AREA)
- Fats And Perfumes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a novel monomer flavor Mal-Val used for cigarettes as well as a preparation method and application thereof. A structure of Mal-Val is shown in the specification. Through physical humectant property tests and inner sensory quality evaluation of the monomer flavor, the monomer flavor is found to have the function of obviously improving the physical humectant properties of cut tobaccos, also have the function of obviously improving the sensory quality of the cigarettes, reduce the irritation and the offensive odor, and improve the mellowness and fullness of the cigarette smoke.
Description
technical field
The invention belongs to essence and flavoring agent and tobacco manufacture field, be specifically related to a kind of Novel tobacco monomer perfume Mal-Val, preparation method and application thereof.
background technology
Along with people are to the attention gradually of smoking and health problem, tar content in cigarette is while reducing further, and 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., this type of humectant object is used to be improve the water ratio of pipe tobacco in the course of processing, improve 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 tobacco monomer perfume Mal-Val, preparation method and application thereof.
For achieving the above object, the present invention adopts following technical scheme:
A kind of cigarette monomer perfume Mal-Val, its structural formula is as follows:
。
The preparation method of described cigarette monomer perfume Mal-Val, it comprises the steps:
After maltose, anhydrous methanol, dimethyl formamide or propylene glycol, reflux 20-40min under 73-88 DEG C of condition, then adds α-amino-isovaleric acid and again to reflux 20-40min, finally add strong-acid ion exchange resin and Quercetin back flow reaction 1-7h; After reaction terminates, be separated and recrystallization and get final product through silica gel column chromatography; Wherein, feed ratio adds 0.130-0.325 gram of α-amino-isovaleric acid, 0.168-0.838 gram Quercetin, 0.035-0.067 gram strong-acid ion exchange resin, 1.8-3.3mL anhydrous methanol, 1.3-3.6mL 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 4:1:1, and developer is ethanol solution of ninhydrin.
Described Mal-Val 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-Val is a kind of aroma compounds of diving, its stable in properties under normal temperature, for the tasteless crystalline substance of white, but it produces tool by heating cleavable and is significantly increased the material of the fragrant and sweet of tobacco and baking perfume as furanone, ketene compounds, 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 Quercetin as inhibitor, react with α-amino-isovaleric acid, successfully synthesize a kind of Maillard reaction intermediate-Mal-Val, 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-Val 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-Val 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 of the present invention due to obvious to the action effect of tobacco product, the bright prospects that therefore there is significant industrial application value He apply.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of target product Mal-Val;
Fig. 2 is the high resolution mass spectrum figure of target product Mal-Val;
Fig. 3 is the carbon-13 nmr spectra figure of target product Mal-Val.
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 and instrument in embodiment.
Maltose, α-amino-isovaleric acid (99%, Aladdin chemical reagents corporation); Quercetin (HPLC level, Sigma Co., USA); Anhydrous methanol, dehydrated alcohol, dimethyl formamide, propylene glycol, 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 cigarette monomer perfume Mal-Va, it comprises the steps:
1 gram of maltose, 1.3mL dimethyl formamide, 3.3mL anhydrous methanol is added in the there-necked flask with thermometer, prolong, reflux 20min under 73 DEG C of conditions, then add 0.130 gram of α-amino-isovaleric acid again to reflux 20min, finally add 0.035 gram of strong-acid ion exchange resin and 0.168 gram of Quercetin back flow reaction 1h; After reaction terminates, obtain white crystalline target product 0.371 gram through silica gel column chromatography separation, 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 4:1:1, 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 cigarette monomer perfume Mal-Va, it comprises the steps:
1 gram of maltose, 3.2mL dimethyl formamide, 2.0mL anhydrous methanol is added in the there-necked flask with thermometer, prolong, reflux 28min under 81 DEG C of conditions, then add 0.286 gram of α-amino-isovaleric acid again to reflux 28min, finally add 0.05 gram of strong-acid ion exchange resin and 0.662 gram of Quercetin back flow reaction 4 h; After reaction terminates, obtain white crystalline target product 0.848 gram through silica gel column chromatography separation, recrystallization.Wherein, the operating process of column chromatography for separation and recrystallization is with embodiment 1.
embodiment 3
A preparation method of cigarette monomer perfume Mal-Va, it comprises the steps:
1 gram of maltose, 3.6mL propylene glycol and 1.8mL anhydrous methanol is added in the there-necked flask with thermometer, prolong, reflux 40min under 88 DEG C of conditions, then add 0.325 gram of α-amino-isovaleric acid again to reflux 40min, finally add 0.067 gram of strong-acid ion exchange resin and 0.838 gram of Quercetin back flow reaction 7h; After reaction terminates, obtain white crystalline target product 0.597 gram through silica gel column chromatography separation, recrystallization.Wherein, the operating process of column chromatography for separation and recrystallization is with embodiment 1.
(1) structural characterization of target product
By infrared spectra (IR), high resolution mass spectrum (HR-MS), carbon-13 nmr spectra (
13c-NMR) respectively structural characterization is carried out to embodiment gained target product Mal-Val, Mal-Val chemical structural formula 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 1.3396.62cm
-1for the O-H stretching vibration of associated state, describe the existence of hydroxyl; 2934.98cm
-1for the stretching vibration of the carboxylic acid of hydrogen bonded, the existence of carboxylic acid is described; 1731.92cm
-1for the charateristic avsorption band of C=O, 1239.92cm
-1, 1128.12cm
-1and 1071.47cm
-1for the coupling of C-O-C key chattering.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 442.40926, hydrogenated molecule formula is C
17h
32nO
12, can judge that its quasi-molecule is C
17h
31nO
12, its relative molecular weight is 441.40142, and the Theoretical molecular formula of Mal-Val is C
17h
31nO
12, its theoretical Mr 441.40103, therefore, sample molecule elementary composition is consistent with the elementary composition of Mal-Val.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-Ser molecular formula.Tentatively carbon can be attributed to by figure: δ=169.510ppm is C
2 〞, δ=108.468ppm is C
1 ', δ=96.192ppm is C
2, δ=77.469ppm is C
4, δ=77.150ppm is C
5 ', δ=76.830ppm is C
2 ', δ=71.006ppm is C
3 ', δ=70.525ppm is C
4 ', δ=70.366ppm is C
5, δ=70.214ppm is C
3, δ=63.643ppm is C
1 〞, δ=62.851ppm is C
6, δ=61.306ppm is C
6 ', δ=54.285ppm is C
1, δ=27.992ppm is C
3 〞, δ=16.235ppm is C
5 〞, δ=15.949ppm is C
4 〞.From the above mentioned, this
13c-NMR spectrum is coincide with the structure of target compound Mal-Val.
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-Val.
(2) applied research of target product 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-Val 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 4 parts of pipe tobaccos are respectively got, every part of 10g, wherein two parts are placed in relative humidity 45%, in temperature 22 DEG C of encloses containers, other two parts are placed in relative humidity 85%, in temperature 22 DEG C of encloses containers, every 12h weighs once, the change of instant water ratio is analyzed, investigate 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, the physics humid keeping performance effect of target product and propylene glycol sees the following form.
Test-results is known, and 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-Val is best, is secondly propylene glycol; And under the condition of relative humidity 85%, temperature 22 DEG C, the pipe tobacco equilibrium moisture content of adding Mal-Val, 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 target product (Mal-Val) is made into the solution of massfraction 1%.Get the above-mentioned solution containing target product of 0.1g, 5.0g, 10.0g, 15.0g, 20.0g and 25.0g 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 2.0 ‰, occur that spine sense increases, the phenomenon that concentration reduces; When its consumption is 2.0 ‰, sucking quality is best.Therefore, best results when adding 0.2g target product in 100g cigarette, namely optimum consumption is 2.0 ‰.
The perfuming smoking result of table 1 Mal-Val
Claims (3)
1. a cigarette monomer perfume Mal-Val, its structural formula is as follows:
。
2. the preparation method of monomer perfume Mal-Val of cigarette described in claim 1, is characterized in that, comprise the steps:
After maltose, anhydrous methanol, dimethyl formamide or propylene glycol, reflux 20-40min under 73-88 DEG C of condition, then adds α-amino-isovaleric acid and again to reflux 20-40min, finally add strong-acid ion exchange resin and Quercetin back flow reaction 1-7h; After reaction terminates, be separated and recrystallization and get final product through silica gel column chromatography; Wherein, feed ratio adds 0.130-0.325 gram of α-amino-isovaleric acid, 0.168-0.838 gram Quercetin, 0.035-0.067 gram strong-acid ion exchange resin, 1.8-3.3mL anhydrous methanol, 1.3-3.6mL dimethyl formamide or propylene glycol meter according to every 1 gram of maltose.
3. Mal-Val described in claim 1 is as the application of fragrance-enhancing tobacco humectant in cigarette.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410586186.3A CN104341466B (en) | 2014-10-28 | 2014-10-28 | Cigarette monomer perfume Mal Val, preparation method and applications |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410586186.3A CN104341466B (en) | 2014-10-28 | 2014-10-28 | Cigarette monomer perfume Mal Val, preparation method and applications |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104341466A true CN104341466A (en) | 2015-02-11 |
| CN104341466B CN104341466B (en) | 2017-08-29 |
Family
ID=52497989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410586186.3A Active CN104341466B (en) | 2014-10-28 | 2014-10-28 | Cigarette monomer perfume Mal Val, preparation method and applications |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104341466B (en) |
Citations (4)
| 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 |
| 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 |
| 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 |
| CN104114176A (en) * | 2011-12-27 | 2014-10-22 | 森下仁丹株式会社 | Maillard reaction inhibitor |
-
2014
- 2014-10-28 CN CN201410586186.3A patent/CN104341466B/en active Active
Patent Citations (4)
| 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 |
| 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 |
| CN104114176A (en) * | 2011-12-27 | 2014-10-22 | 森下仁丹株式会社 | Maillard reaction inhibitor |
| 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 (4)
| Title |
|---|
| QIN-QIN DU ET AL.: "Studies on structures and activities of initial Maillard reaction products byelectrospray ionisation mass spectrometry combined with liquid chromatographyin processing of red ginseng", 《FOOD CHEMISTRY》 * |
| 王华: "烟保润剂浅析", 《轻工科技》 * |
| 程军等: "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", 《浙江大学学报（农业与生命科学版）》 * |
| 郑毅男等: "红参中新化合物精氨酸苷的生成机理及生成条件的研究", 《中国药物化学杂志》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104341466B (en) | 2017-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103349356B (en) | Cigarette flavouring humectant 1-L-leucine-1-deoxidation-D-Fructose and preparation method thereof | |
| CN102304155B (en) | Monosaccharide geraniol carbonate diester compound, preparation method and use thereof | |
| CN110862366B (en) | Milk-flavored tobacco sweetener, preparation method and application thereof in cigarettes | |
| CN105017190A (en) | Preparation method and use of benzolactone compound in tobacco | |
| CN102286035B (en) | Bimenthoxycarbonylmonose ester compound as well as preparation method and application thereof | |
| CN102311464B (en) | Monomenthyloxycarbonyl monosugar ester compounds, preparation method thereof and purpose thereof | |
| CN103351417B (en) | A kind of cigarette flavouring humectant 1-L-tryptophane-1-deoxidation-D-Fructose and preparation method thereof | |
| CN105481818A (en) | Aroma-enhancing moisture-retaining isocoumarin compound, and preparation method and application thereof | |
| CN106380473B (en) | A kind of lactone compound, preparation method and use | |
| CN104370986A (en) | Saccharide-derived flavor-enhancing humectant Mal-Pro for cigarettes, and preparation method and application thereof | |
| Moldoveanu et al. | An LC-MS method for the analysis of some organic acids in tobacco leaf, snus, and wet snuff | |
| CN104370979A (en) | Cigarette monomer spice Mal-Ser as well as preparation method and application thereof | |
| CN104341461A (en) | Monomer flavor Mal-Thr used for cigarettes as well as preparation method and application thereof | |
| CN104311609B (en) | Cigarette monomer perfume Mal-Leu, preparation method and applications | |
| CN111072614B (en) | Lipid wax flavored tobacco sweetener, preparation method and application thereof in cigarettes | |
| CN104311608A (en) | Hydrophilic aroma-enhancing humectant Mal-Hyp for tobacco, preparation method and application of humectant | |
| CN104341465A (en) | Hydrophilic tobacco aroma enhancing humectant Mal-Ala as well as preparation method and application thereof | |
| CN104341466A (en) | Monomer flavor Mal-Val used for cigarettes as well as preparation method and application thereof | |
| CN110963987A (en) | Sour-flavor tobacco sweetener, preparation method and application in cigarettes | |
| CN104341467A (en) | Monomer flavor Mal-Amb used for cigarettes as well as preparation method and application thereof | |
| CN104341463A (en) | Monomer flavor Mal-Ile used for cigarettes as well as preparation method and application thereof | |
| CN104031162B (en) | Radix Ophiopogonis polysaccharide, method for extraction and purification and the application as tobacco humectant thereof | |
| CN104356174A (en) | Monomer spice Mal-Phe for tobacco as well as preparation method and application of monomer spice | |
| CN104341462A (en) | Sugar derived aroma enhancing humectant Mal-Trp used for tobaccos as well as preparation method and application thereof | |
| CN104341464A (en) | Hydrophilic tobacco aroma enhancing humectant Mal-Gly as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
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. |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |