CN104311609A - Monomeric spice Mal-Leu for cigarette as well as preparation method and application of monomeric spice Mal-Leu - Google Patents
Monomeric spice Mal-Leu for cigarette as well as preparation method and application of monomeric spice Mal-Leu Download PDFInfo
- Publication number
- CN104311609A CN104311609A CN201410586175.5A CN201410586175A CN104311609A CN 104311609 A CN104311609 A CN 104311609A CN 201410586175 A CN201410586175 A CN 201410586175A CN 104311609 A CN104311609 A CN 104311609A
- Authority
- CN
- China
- Prior art keywords
- leu
- mal
- cigarette
- spice
- monomeric
- 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
- Fats And Perfumes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of essence spices and tobacco processing, and particularly relates to monomeric spice Mal-Leu for cigarette as well as a preparation method and an application of the monomeric spice Mal-Leu. The structural formula of the monomeric spice Mal-Leu for cigarette is as shown in the specification. According to the invention, physical moisture retention property test of the monomeric spice and inherent sensory quality evaluation of finished product cigarette are performed, so that the monomeric spice Mal-Leu can not only obviously improve the physical moisture retention property of the cut tobacco, has the effect of significantly improving the sensory quality of the cigarette, is capable of reducing the stimulation and miscellaneous gas of the cigarette and enhancing the mellow sense of cigarette.
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-Leu, preparation method and application.
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 object to be improve pipe tobacco water ratio and pipe tobacco degrading resistance property in the course of processing, 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-Leu, preparation method and application thereof.
For achieving the above object, the present invention adopts following technical scheme:
A kind of cigarette monomer perfume Mal-Leu, its structural formula is as follows:
。
The preparation method of described cigarette monomer perfume Mal-Leu, it comprises the steps:
By maltose, anhydrous methanol and dimethyl formamide or mixed with propylene glycol and the 23-43min that refluxes under 75-89 DEG C of condition, then add leucine again to reflux 23-43min, finally add strong-acid ion exchange resin and ampelopsin back flow reaction 1.5-7.5h; 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 leucine, 0.339-1.694 gram ampelopsin, 0.033-0.065 gram strong-acid ion exchange resin, 1.6-3.0mL anhydrous methanol, 1.5-3.8mL dimethyl formamide or propylene glycol meter according to every 1 gram of maltose.
Column chromatography for separation elutriant used is the mixing solutions be made up of propyl carbinol, glacial acetic acid and water, and the volume ratio of three is 5:2:1, and developer is ethanol solution of ninhydrin.
Described Mal-Leu 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-Leu is a kind of latent aroma compounds, is white tasteless crystalline substance under normal temperature, stable in properties, but it is significantly increased the material of the fragrant and sweet of tobacco and baking perfume as furanone, ketene compounds by heating cleavable generation tool.In addition, itself contain a large amount of hydrophilic radical, this compound is still rare at present as fragrance-enhancing tobacco humectant.
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 ampelopsin as inhibitor, react with leucine with solid acid, successfully synthesizes a kind of Studies of The Aromatic Substances-Mal-Leu that dives, studies and determine synthesis technology condition and preferred plan.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 tobacco monomer perfume, first Mal-Leu is applied in cigarette as fragrance-enhancing tobacco humectant, by the test of cigarette physics humid keeping performance and the inherent sensory quality assessment of cigarette, result shows that it has excellent physics humectation effect to pipe tobacco, and the pungency of cigarette 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-Leu 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-Leu;
Fig. 2 is the high resolution mass spectrum figure of target product Mal-Leu;
Fig. 3 is the carbon-13 nmr spectra figure of target product Mal-Leu.
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, leucine (99%, Aladdin chemical reagents corporation); Ampelopsin (HPLC level, French Extrasynthese company); 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-Leu, it comprises the steps:
1 gram of maltose, 1.5mL dimethyl formamide, 3.0mL anhydrous methanol is added in the there-necked flask with thermometer, prolong, reflux 23min under 75 DEG C of conditions, then add 0.146 gram of leucine again to reflux 23min, finally add 0.033 gram of strong-acid ion exchange resin and 0.339 gram of ampelopsin back flow reaction 1.5h; White crystalline target product 0.366 gram is obtained through silica gel column chromatography separation and recrystallization after reaction terminates; 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 5:2:1, 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 cigarette monomer perfume Mal-Leu, it comprises the steps:
1 gram of maltose, 3.4mL dimethyl formamide, 2.1mL anhydrous methanol is added in the there-necked flask with thermometer, prolong, reflux 29min under 82 DEG C of conditions, then add 0.268 gram of leucine again to reflux 29min, finally add 0.055 gram of strong-acid ion exchange resin and 1.016 grams of ampelopsin back flow reaction 3.5 h; White crystalline target product Mal-Leu 0.819 gram is obtained through silica gel column chromatography separation and recrystallization after reaction terminates.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-Leu, it comprises the steps:
1 gram of maltose, 3.8mL propylene glycol and 1.6mL anhydrous methanol is added in the there-necked flask with thermometer, prolong, reflux 43min under 89 DEG C of conditions, then add 0.364 gram of leucine again to reflux 43min, finally add 0.065 gram of strong-acid ion exchange resin and 1.694 grams of ampelopsin back flow reaction 7.5h; White crystalline target product 0.605 gram is obtained through silica gel column chromatography separation and recrystallization after reaction terminates.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-Leu, the chemical structural formula of Mal-Leu 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 1.3510.93cm
-1and 3199.47cm
-1for the stretching vibration of the carboxylic acid of hydrogen bonded, describe the existence of carboxylic acid; 2988.85cm
-1and 2937.98cm
-1for saturated hydrocarbyl C-H stretching vibration, 1740.77cm
-1for the charateristic avsorption band of C=O, 1213.09cm
-1, 1167.28cm
-1, 1111.94cm
-1and 1070.93cm
-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 50V% 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 456.43367, hydrogenated molecule formula is C
18h
34nO
12, can judge that its quasi-molecule is C
18h
33nO
12, its relative molecular weight is 455.42583, and the Theoretical molecular formula of Mal-Leu is C
18h
33nO
12, its theoretical Mr 455.42631, therefore, sample molecule elementary composition is consistent with the elementary composition of Mal-Leu.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, 18 the spectrum peaks provided in figure represent the carbon atom that in molecule, 18 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 1:1:1:1:1:1:1:1:1:1:1:1:1:1:1:1:1:1, its digital sum is 18, consistent with carbon atom number in Mal-Leu molecular formula.Tentatively carbon can be attributed to by figure: δ=174.783ppm is C
6 〞, δ=101.066ppm is C
1 ', δ=97.972ppm is C
2, δ=80.936ppm is C
4, δ=76.358ppm is C
5 ', δ=74.520ppm is C
2 ', δ=73.203ppm is C
3 ', δ=72.490ppm is C
4 ', δ=69.703ppm is C
5, δ=69.389ppm is C
3, δ=63.671ppm is C
6, δ=62.578ppm is C
6 ', δ=61.031ppm is C
1 〞, δ=52.498ppm is C
1, δ=43.319ppm is C
2 〞, δ=23.314ppm is C
3 〞, δ=21.055ppm is C
4 〞, δ=20.516ppm is C
5 〞.From the above mentioned, this
13c-NMR spectrum is coincide with the structure of target compound Mal-Leu.
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-Leu.
(2) target productmal-Leu
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-Leu 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%, temperature 22 DEG C of fixed temperature and humidity test experiments case test environments, and 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, the change of instant water ratio is analyzed, 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-Leu 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-Leu, 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-Leu) is made into the solution of massfraction 1%.Get the above-mentioned solution containing target product of 0.50g, 2.50g, 5.00g, 10.00g, 15.00g and 20.00g 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 in 100g cigarette, namely optimum consumption is 1.5 ‰.
The perfuming smoking result of table 1 Mal-Leu
Claims (3)
1. a cigarette monomer perfume Mal-Leu, its structural formula is as follows:
。
2. the preparation method of monomer perfume Mal-Leu of cigarette described in claim 1, is characterized in that, comprise the steps:
By maltose, anhydrous methanol and dimethyl formamide or mixed with propylene glycol and the 23-43min that refluxes under 75-89 DEG C of condition, then add leucine again to reflux 23-43min, finally add strong-acid ion exchange resin and ampelopsin back flow reaction 1.5-7.5h; 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 leucine, 0.339-1.694 gram ampelopsin, 0.033-0.065 gram strong-acid ion exchange resin, 1.6-3.0mL anhydrous methanol, 1.5-3.8mL dimethyl formamide or propylene glycol meter according to every 1 gram of maltose.
3. Mal-Leu 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 |
|---|---|---|---|
| CN201410586175.5A CN104311609B (en) | 2014-10-28 | 2014-10-28 | Cigarette monomer perfume Mal-Leu, preparation method and applications |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410586175.5A CN104311609B (en) | 2014-10-28 | 2014-10-28 | Cigarette monomer perfume Mal-Leu, preparation method and applications |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104311609A true CN104311609A (en) | 2015-01-28 |
| CN104311609B CN104311609B (en) | 2016-08-24 |
Family
ID=52366945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410586175.5A Active CN104311609B (en) | 2014-10-28 | 2014-10-28 | Cigarette monomer perfume Mal-Leu, preparation method and applications |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104311609B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061178A (en) * | 2015-08-21 | 2015-11-18 | 云南中烟工业有限责任公司 | Sesquiterpenoids in tobacco and preparing method and application thereof |
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 |
| CN101787329A (en) * | 2010-03-10 | 2010-07-28 | 广东中烟工业有限责任公司 | Tobacco flavor as well as preparation method and application thereof |
| US20130196935A1 (en) * | 2012-01-27 | 2013-08-01 | Animal Cell Therapies Inc. | Synthetic glycoamine compounds |
| 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 |
-
2014
- 2014-10-28 CN CN201410586175.5A patent/CN104311609B/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 |
| CN101787329A (en) * | 2010-03-10 | 2010-07-28 | 广东中烟工业有限责任公司 | Tobacco flavor as well as preparation method and application thereof |
| US20130196935A1 (en) * | 2012-01-27 | 2013-08-01 | Animal Cell Therapies Inc. | Synthetic glycoamine compounds |
| 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 (1)
| Title |
|---|
| GENNADI V. GLINSKY，等: ""Inhibition of colony formation in agarose of metastatic human breast carcinoma and melanoma cells by synthetic glycoamine analogs"", 《CLINICAL & EXPERIMENTAL METASTASIS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061178A (en) * | 2015-08-21 | 2015-11-18 | 云南中烟工业有限责任公司 | Sesquiterpenoids in tobacco and preparing method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104311609B (en) | 2016-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103349356B (en) | Cigarette flavouring humectant 1-L-leucine-1-deoxidation-D-Fructose and preparation method thereof | |
| Risley et al. | Oxygen-18 isotope effect in carbon-13 nuclear magnetic resonance spectroscopy. 2. The effect of structure | |
| CN105017190A (en) | Preparation method and use of benzolactone compound in tobacco | |
| Ernst et al. | Isolation and identification of a new, naturally occurring cytokinin (6-benzylaminopurineriboside) from an anise cell culture (Pimpinella anisum L.) | |
| CN102286035B (en) | Bimenthoxycarbonylmonose ester compound as well as preparation method and application thereof | |
| CN110862366A (en) | Milk-flavor tobacco sweetener, preparation method and application in cigarettes | |
| CN105481818A (en) | Aroma-enhancing moisture-retaining isocoumarin compound, and preparation method and application thereof | |
| CN104370986A (en) | Saccharide-derived flavor-enhancing humectant Mal-Pro for cigarettes, and preparation method and application thereof | |
| CN104311609A (en) | Monomeric spice Mal-Leu for cigarette as well as preparation method and application of monomeric spice Mal-Leu | |
| CN103409238A (en) | Cut stem fumet for tobacco 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 | |
| CN104370979A (en) | Cigarette monomer spice Mal-Ser as well as preparation method and application thereof | |
| 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 | |
| CN110963987A (en) | Sour-flavor tobacco sweetener, preparation method and application in cigarettes | |
| CN104356174A (en) | Monomer spice Mal-Phe for tobacco as well as preparation method and application of monomer spice | |
| CN104341466A (en) | Monomer flavor Mal-Val 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 | |
| CN104341464A (en) | Hydrophilic tobacco aroma enhancing humectant Mal-Gly as well as preparation method and application thereof | |
| CN104341467A (en) | Monomer flavor Mal-Amb used for cigarettes as well as preparation method and application thereof | |
| CN104341462A (en) | Sugar derived aroma enhancing humectant Mal-Trp used for tobaccos 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 | |
| CN105146744B (en) | Carboxy methylation lentinan as tobacco humectant application | |
| CN103467535B (en) | A kind of humectant for smoke 1-O-hydroxyethyl-D-Fructose and preparation method 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |