CN104341461B - Cigarette monomer perfume Mal Thr, preparation method and applications - Google Patents

Abstract

The present invention relates to a kind of Novel tobacco monomer perfume Mal Thr, preparation method and applications.The Mal Thr structures are as follows：

Description

Cigarette monomer perfume Mal-Thr, preparation method and applications

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-Thr, 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-Thr, 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-Thr, its structural formula is as follows：

。

Cigarette monomer perfume Mal-Thr preparation method, it comprises the following steps：

Flow back 20- by maltose, absolute methanol, dimethylformamide or mixed with propylene glycol and under the conditions of 75-89 DEG C 50min, then adds threonine and flows back again 20-50min, be eventually adding strong-acid ion exchange resin and myricetin backflow 1-8.5h is reacted, reaction separates and be recrystallized to give target product through silica gel column chromatography after terminating；Wherein, rate of charge is according to every 1 Gram maltose add 0.132-0.331 grams of threonine, 0.326-1.619 grams of myricetin, 0.032-0.062 grams of highly acid from Sub-exchange resin, 1.6-3.0mL absolute methanols, 1.5-3.8mL 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 5：2：1, developer is ethanol solution of ninhydrin.

Applications of the Mal-Thr 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-Thr 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 myricetin as inhibitor, with Soviet Union Propylhomoserin reacts, and successfully synthesizes a kind of latent Studies of The Aromatic Substances-Mal-Thr, 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-Thr 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-Thr 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-Thr infrared spectrogram；

Fig. 2 is target product Mal-Thr high resolution mass spectrum figure；

Fig. 3 is target product Mal-Thr 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, threonine（99%, Aladdin chemical reagents corporation）；Myricetin（HPLC grades, French Extrasynthese Company）；Absolute methanol, absolute ethyl alcohol, dimethylformamide, propane diols, n-butanol, glacial acetic acid（Learn examination in AR, triumphant Tonghua, Tianjin Agent Co., Ltd）；Amberlite IR-120 (H) ion exchange resin（Alfa Aesar）；Silica gel（Chemical pure, Qingdao Haiyang 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-Thr preparation method, it comprises the following steps：

1 gram of maltose, 1.5mL dimethylformamides, 3.0mL are added in thermometer, the three-necked flask of condenser pipe Absolute methanol, flow back 20min under the conditions of 75 DEG C, then adds 0.132 gram of threonine and flows back again 20min, is eventually adding 0.032 gram of strong-acid ion exchange resin and 0.326 gram of myricetin back flow reaction 1h；After reaction terminates, through silica gel column chromatography point From, be recrystallized to give 0.293 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 5：2：1, 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-Thr preparation method, it comprises the following steps：

1 gram of maltose, 3.4mL dimethylformamides, 2.1mL are added in thermometer, the three-necked flask of condenser pipe Absolute methanol, flow back 36min under the conditions of 82 DEG C, then adds 0.266 gram of threonine and flows back again 36min, is eventually adding 0.056 gram of strong-acid ion exchange resin and 1.015 grams of h of myricetin back flow reaction 3.5；After reaction terminates, through silica gel column chromatography Separate, be recrystallized to give 0.867 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-Thr preparation method, it comprises the following steps：

1 gram of maltose, 3.8mL propane diols and 1.6mL are added in thermometer, the three-necked flask of condenser pipe without water beetle Alcohol, flow back 50min under the conditions of 89 DEG C, then adds 0.331 gram of threonine and flows back again 50min, is eventually adding 0.062 gram strong Acid-exchange resin and 1.619 grams of myricetin back flow reaction 8.5h；After reaction terminates, separate, tie again through silica gel column chromatography Crystalline substance obtains 0.535 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-Thr and carry out structural characterization, Mal-Thr 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.As shown in the drawing, 3377.59cm^-1 For the stretching vibration peak for hydroxyl associated state; 2972.18cm^-1For alkyl stretching vibration peak；1582.60cm^-1For carbonyl double bond characteristic peak,.Thus the thing can be primarily determined that Matter 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 444.38303, hydrogenation Molecular formula is C₁₆H₃₀NO₁₃, can determine whether its quasi-molecule is C₁₆H₂₉NO₁₃, its relative molecular weight is 443.37519, and Mal-Thr Theoretical molecular formula is C₁₆H₂₉NO₁₃, its theoretical Mr 443.37478, therefore, sample molecule elemental constituent and Mal-Thr 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 16 spectral peaks provided in figure represent 16 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, its digital sum is 16, consistent with carbon atom number in Mal-Thr molecular formula.Tentatively carbon can be returned by figure Belong to and be：δ=168.921ppm is C^4〞, δ=102.390ppm is C^1′, δ=98.646ppm is C², δ=77.949ppm is C⁴, δ= 77.034ppm for C^5′, δ=76.714ppm is C^2′, δ=73.048ppm is C^3′, δ=71.927ppm is C^1〞, δ=70.898ppm is C^4′, δ=69.226ppm is C⁵, δ=68.405ppm is C³, δ=66.820ppm is C^2〞, δ=64.512ppm is C⁶, δ= 62.082ppm for C^6′, δ=55.857ppm is C¹, δ=18.082ppm is C^3〞From the above mentioned, this¹³C-NMR is composed and object Mal- Thr 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-Thr.

（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-Thr 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-Thr 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-Thr 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 target product（Mal-Thr）It is made into the solution of mass fraction 1%.Take respectively The above-mentioned solution containing target product of 0.5g, 1.0g, 5.0g, 10.0g, 15.0g, 20.0g and 25.0g, then uniform spray is added to seven In the 100g blank cigarette shreds of the non-flavoring and casing of part, roll, respectively pick out 100 same weight cigarette, be placed in 22 DEG C of temperature ± 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 is equally identical 48h is balanced under the conditions of 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 Mal-Thr of table 1 perfuming smoking result

Claims (2)

1. a kind of cigarette monomer perfume Mal-Thr preparation method, it is characterised in that cigarette monomer perfume Mal-Thr knot Structure formula is as follows：

；

Specifically include following steps：

Flow back 20- by maltose, absolute methanol, dimethylformamide or mixed with propylene glycol and under the conditions of 75-89 DEG C 50min, then adds threonine and flows back again 20-50min, be eventually adding strong-acid ion exchange resin and myricetin backflow 1-8.5h is reacted, reaction separates and be recrystallized to give target product through silica gel column chromatography after terminating；Wherein, rate of charge is according to every 1 Gram maltose add 0.132-0.331 grams of threonine, 0.326-1.619 grams of myricetin, 0.032-0.062 grams of highly acid from Sub-exchange resin, 1.6-3.0mL absolute methanols, 1.5-3.8mL dimethylformamides or propane diols meter.

2. the cigarette prepared using preparation method described in claim 1 is with monomer perfume Mal-Thr as fragrance-enhancing tobacco humectation Application of the agent in cigarette.