CN106496147B - The preparation method and applications of the latent fragrant monomer 5- methylpyrazine -2- formate ester of cigarette - Google Patents
The preparation method and applications of the latent fragrant monomer 5- methylpyrazine -2- formate ester of cigarette Download PDFInfo
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- CN106496147B CN106496147B CN201610880105.XA CN201610880105A CN106496147B CN 106496147 B CN106496147 B CN 106496147B CN 201610880105 A CN201610880105 A CN 201610880105A CN 106496147 B CN106496147 B CN 106496147B
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- cigarette
- methylpyrazine
- formic acid
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- -1 5- methylpyrazine -2- formate ester Chemical class 0.000 title claims abstract description 47
- 235000019504 cigarettes Nutrition 0.000 title claims abstract description 38
- 239000000178 monomer Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 33
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 29
- RBYJWCRKFLGNDB-UHFFFAOYSA-N 5-methylpyrazine-2-carboxylic acid Chemical compound CC1=CN=C(C(O)=O)C=N1 RBYJWCRKFLGNDB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 241000208125 Nicotiana Species 0.000 claims abstract description 15
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000012074 organic phase Substances 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 14
- 239000012043 crude product Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims abstract description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000012544 monitoring process Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000004440 column chromatography Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000000654 additive Substances 0.000 claims abstract description 4
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- 239000007832 Na2SO4 Substances 0.000 claims abstract description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 20
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- CAWHJQAVHZEVTJ-UHFFFAOYSA-N methylpyrazine Chemical group CC1=CN=CC=N1 CAWHJQAVHZEVTJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002304 perfume Substances 0.000 claims description 10
- 239000005792 Geraniol Substances 0.000 claims description 8
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 claims description 8
- 229940113087 geraniol Drugs 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- UFLHIIWVXFIJGU-ARJAWSKDSA-N (Z)-hex-3-en-1-ol Chemical compound CC\C=C/CCO UFLHIIWVXFIJGU-ARJAWSKDSA-N 0.000 claims 1
- 235000002639 sodium chloride Nutrition 0.000 claims 1
- 230000007794 irritation Effects 0.000 abstract description 2
- 239000000779 smoke Substances 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 239000003205 fragrance Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000796 flavoring agent Substances 0.000 description 5
- 235000019634 flavors Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- CNOPDZWOYFOHGN-BQYQJAHWSA-N Beta-Ionol Chemical compound CC(O)\C=C\C1=C(C)CCCC1(C)C CNOPDZWOYFOHGN-BQYQJAHWSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- CNOPDZWOYFOHGN-UHFFFAOYSA-N beta-ionol Natural products CC(O)C=CC1=C(C)CCCC1(C)C CNOPDZWOYFOHGN-UHFFFAOYSA-N 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000000391 smoking effect Effects 0.000 description 2
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 1
- OBHGOXFSRVNKBS-AATRIKPKSA-N 2,4,4-trimethyl-3-[(e)-3-oxobut-1-enyl]cyclohex-2-en-1-one Chemical compound CC(=O)\C=C\C1=C(C)C(=O)CCC1(C)C OBHGOXFSRVNKBS-AATRIKPKSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000007073 chemical hydrolysis Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 230000009189 diving Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- FQMZVFJYMPNUCT-UHFFFAOYSA-N geraniol formate Natural products CC(C)=CCCC(C)=CCOC=O FQMZVFJYMPNUCT-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008774 maternal effect Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 229930003658 monoterpene Natural products 0.000 description 1
- 235000002577 monoterpenes Nutrition 0.000 description 1
- 229960002715 nicotine Drugs 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D241/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile 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
- A24B15/38—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring having only nitrogen as hetero atom
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B3/00—Preparing tobacco in the factory
- A24B3/12—Steaming, curing, or flavouring tobacco
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Plural Heterocyclic Compounds (AREA)
- Fats And Perfumes (AREA)
Abstract
A kind of preparation method of the latent fragrant monomer 5- methylpyrazine -2- formate ester of cigarette, include the following steps: that 5- methylpyrazine -2- formic acid and single hydroxyl alcohol is taken to be dissolved in dry methylene chloride, stir one section of 10min-30min, 4-dimethylaminopyridine (DMAP) and 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl) is added, 4-12h is stirred at room temperature, TLC monitoring reaction, track reaction end, add water washing into organic phase, liquid separation, it is washed again with saturated sodium chloride solution, liquid separation, organic phase anhydrous Na2SO4It is dry, it is concentrated to give crude product, carries out column chromatography for separation then up to the product.Product prepared by the present invention can significantly improve the additive amount in cigarette, and the outer fragrant kind without influencing cigarette is applied in cigarette as fragrance-enhancing tobacco agent, can reduce the irritation and miscellaneous gas, the mellow and full sense of raising cigarette smoke and comfort of cigarette.
Description
Technical field
The present invention relates to flavors and fragrances and tobacco manufacture field, the latent fragrant monomer 5- methylpyrazine -2- of specifically a kind of cigarette
The preparation method and applications of formate ester.
Background technique
Many excellent fragrance due to its high high-temp stability is poor, volatility compared with strong, fragrance remaining time is short the problems such as limit
It is widely applied.Latent Studies of The Aromatic Substances is that a kind of relative molecular mass is big, the higher substance of boiling point, and fragrance is less or itself is without perfume
Gas, but can release by the approach such as chemical hydrolysis, enzymatic hydrolysis or microbial action, pyrolysis, photodestruciton with fragrance fragrance
Compound.Because its safety is preferable, it is included in natural perfume material scope in the world, deploys certain flavor edible essence effects with it
Very well.Different from volatility and half volatile fragrance matter, perfume class compound of diving is reducing artificial flavor and taste compensation trace
It not will lead to the significant changes of the substances delivering amount such as nicotine in cigarette mainstream flue gas, tar simultaneously, it can more longlasting stable offer cigarette
Gas characteristic chicken flavor.In the prior art, latent Studies of The Aromatic Substances is widely applied in the adding technology of cigarette shreds, and the present invention provides one
The preparation method of the latent fragrant monomer 5- methylpyrazine -2- formate ester of kind cigarette, and inquire into its application in perfuming cigarette.
Summary of the invention
The present invention provides a kind of new cigarette latent perfume monomer 5- methylpyrazine-to develop novel cigarette flavor precursors
The preparation method of 2- formate ester and its application in cigarette.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of cigarette preparation method of monomer perfume 5- methylpyrazine -2- formic acid esters, includes the following steps:
It takes 5- methylpyrazine -2- formic acid and single hydroxyl alcohol to be dissolved in dry methylene chloride, stirs one section of 10min-
4-dimethylaminopyridine (DMAP) and 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate is added in 30min
(EDCHCl), 4-12h is stirred at room temperature, (petroleum ether: ethyl acetate=10:1, Rf=0.5, ultraviolet 254nm are aobvious for TLC monitoring reaction
Color), track reaction end.Add water washing, liquid separation into organic phase, then washed with saturated sodium chloride solution, liquid separation, organic phase is used
Anhydrous Na2SO4It is dry, it is concentrated to give crude product, then column chromatographic analysis carries out column chromatography for separation up to the latent fragrant monomer of the cigarette
5- methylpyrazine -2- formate ester.
Further, the column chromatography for separation eluent is ethyl acetate and petroleum ether, the volume ratio 100:1- of the two
20:1。
Further, the molar ratio of the 5- methylpyrazine -2- formic acid and single hydroxyl alcohol 0.9:1-1:0.9 it
Between.
Further, the single hydroxyl alcohol is that geraniol or ionol are obtained when single hydroxyl alcohol is geraniol
Product is 5- methylpyrazine -2- formic acid spiceleaf alcohol ester, and when single hydroxyl alcohol is ionol, obtained product is 5- methyl pyrrole
Piperazine -2- formic acid-β-ionol esters, the two structural formula are as follows:
Further, the cigarette of method preparation as described above uses monomer perfume 5- methylpyrazine -2- formate ester as tobacco
Application of the fumet in cigarette is applied in cigarette as fragrance-enhancing tobacco agent, and additive amount is the 0.01- of pipe tobacco weight
0.05%.
The compounds of this invention 5- methylpyrazine -2- formic acid spiceleaf alcohol ester and 5- methylpyrazine -2- formic acid-β-ionol esters
For a kind of latent aroma compounds, its property is stablized under room temperature, is colourless liquid, but it is generated by heating cleavable has obvious increase
Add tobacco aroma substance.Such as 3- oxo-beta-ionone, geraniol, pyrazine, monoterpene vinyl compound.
Compared to the prior art, beneficial effects of the present invention:
1. present invention preparation 5- methylpyrazine -2- formic acid spiceleaf alcohol ester and 5- methylpyrazine -2- formic acid-β-ionol esters
Compared with geraniol and β-ionol maternal body, the additive amount in cigarette can be significantly improved, the outer perfume (or spice) without influencing cigarette
Kind.
2. the present invention is with 4-dimethylaminopyridine/1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate
5- methylpyrazine -2- formic acid and geraniol, β-ionol esterification reaction condensation reagent, can significantly improve reaction yield, letter
Change aftertreatment technology.
3. two kinds of cigarette monomer perfumes that the present invention develops are applied in cigarette as fragrance-enhancing tobacco agent for the first time,
The irritation and miscellaneous gas, the mellow and full sense of raising cigarette smoke and comfort of cigarette can be reduced.
Detailed description of the invention
Fig. 1 is 5- methylpyrazine -2- formic acid spiceleaf alcohol ester 1H NMR nuclear magnetic spectrogram；
Fig. 2 is 5- methylpyrazine -2- formic acid spiceleaf alcohol ester 13C NMR nuclear magnetic spectrogram；
Fig. 3 is 5- methylpyrazine -2- formic acid spiceleaf alcohol ester HRMS high-resolution spectrogram；
Fig. 4 is 5- methylpyrazine -2- formic acid-β-ionol 1H NMR nuclear magnetic spectrogram；
Fig. 5 is 5- methylpyrazine -2- formic acid-β-ionol 13C NMR nuclear magnetic spectrogram；
Fig. 6 is 5- methylpyrazine -2- formic acid-β-ionol HRMS high-resolution spectrogram.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below, convenient for being well understood in of the invention
Hold, but they limiting the invention.
Embodiment one
The preparation method of tobacco aromaticss monomer 5- methylpyrazine -2- formic acid spiceleaf alcohol ester:
10mmol geraniol and 10mmol5- methylpyrazine -2- formic acid is taken to be dissolved in the dry methylene chloride of 100ml, stirring
After 10min, 4-dimethylaminopyridine (DMAP) (5mmol) and 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimine is added
Hydrochloride (EDCHCl) (11mmol), is stirred at room temperature, and TLC monitoring reaction tracks reaction end.Into organic phase plus water 50mL is washed
It washs, liquid separation, then is washed with 50mL saturated sodium chloride solution, liquid separation, organic phase is dry with anhydrous Na 2SO4, is concentrated to give crude product.
Crude product 50mL methylene chloride dissolves, and the silica gel 4g of 100-200 mesh is added, decompression is spin-dried for mixing sample, with 80g 100-200 purpose
With petroleum ether in silica gel column chromatography strain: ethyl acetate=60:1 is slowly eluted, be concentrated, dry after obtain target product.
Embodiment two
The preparation method of tobacco aromaticss monomer 5- methylpyrazine -2- formic acid spiceleaf alcohol ester:
It takes 10mmol geraniol and 1.05mmol5- methylpyrazine -2- formic acid to be dissolved in the dry methylene chloride of 100ml, stirs
After mixing 10min, it is sub- that 4-dimethylaminopyridine (DMAP) (4mmol) and 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne two is added
Amine hydrochlorate (EDCHCl) (11mmol), is stirred at room temperature, and TLC monitoring reaction tracks reaction end.Add water 50mL into organic phase
Washing, liquid separation, then washed with 50mL saturated sodium chloride solution, liquid separation, organic phase is dry with anhydrous Na 2SO4, is concentrated to give thick production
Object.Crude product 50mL methylene chloride dissolves, and the silica gel 4g of 100-200 mesh is added, decompression is spin-dried for mixing sample, with 80g 100-200
With petroleum ether in purpose silica gel column chromatography strain: ethyl acetate=60:1 is slowly eluted, be concentrated, dry after obtain target product.
Embodiment three
Tobacco aromaticss monomer 5- methylpyrazine -2- formic acid-β-ionol esters preparation method:
In three-necked flask, weighed 20mmol β-ionol is added and 10mmol 5- methylpyrazine -2- formic acid is dissolved in
In 200ml dry methylene chloride, after stirring 10min, 4-dimethylaminopyridine (DMAP) (10mmol) and 1- ethyl-is added
(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl) (22mmol), is stirred at room temperature, TLC monitoring reaction,
Tracking reaction is to terminal.Into organic phase plus pure water 100mL is washed, liquid separation, then is washed with 100mL saturated sodium chloride solution,
Liquid separation, organic phase is dry with anhydrous Na 2SO4, the crude product of concentration.Crude product 10mL methylene chloride dissolves, and 100-200 is added
Purpose silica gel 7g, decompression is spin-dried for mixing sample, with the silica gel column chromatography post separation of 100g 100-200 mesh, eluant, eluent petroleum ether: acetic acid
Ethyl ester=80:1 is slowly eluted, be concentrated, dry after obtain target product
Example IV
Tobacco aromaticss monomer 5- methylpyrazine -2- formic acid-β-ionol esters preparation method:
In three-necked flask, weighed 20mmol β-ionol is added and 21mmol 5- methylpyrazine -2- formic acid is dissolved in
In 200ml dry methylene chloride, after stirring 10min, 4-dimethylaminopyridine (DMAP) (8mmol) and 1- ethyl-(3- is added
Dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl) (22mmol), is stirred, TLC monitoring reaction, tracking at room temperature
Reaction is to terminal.Into organic phase plus pure water 100mL is washed, liquid separation, then is washed with 100mL saturated sodium chloride solution, liquid separation,
Organic phase is dry with anhydrous Na 2SO4, the crude product of concentration.Crude product 10mL methylene chloride dissolves, and 100-200 purpose is added
Silica gel 7g, decompression is spin-dried for mixing sample, with the silica gel column chromatography post separation of 100g 100-200 mesh, eluant, eluent petroleum ether: ethyl acetate
=80:1 is slowly eluted, be concentrated, dry after obtain target product
(1) structural characterization of target product
As red high resolution mass spectrum (HR-MS), carbon-13 nmr spectra (1H-NMR13C-NMR) respectively to mesh obtained by embodiment
It marks product 5- methylpyrazine -2- formic acid spiceleaf alcohol ester and 5- methylpyrazine -2- formic acid-β-ionol esters carries out structural characterization,
Specific data are as follows:
As shown in Figure 1-3,5- methylpyrazine -2- geranyl formate: colourless oil liquid.1H NMR(400MHz,CDCl3)δ
Ppm 9.19 (s, 1H), 8.58 (s, 1H), 5.52 (q, J=.73,6.67,6.67Hz, 1H), 5.09 (t, J=11.66,
11.66Hz, 1H), 4.94 (dd, J=14.98,7.25Hz, 2H), 2.67 (s, 3H), 2.23-2.02 (m, 4H), 1.82-1.76
(m,3H),1.67(s,3H),1.60(s,3H)；13C NMR(400MHz,CDCl3)δppm 164.23,157.64,145.36,
144.23,143.30,140.80,131.87,123.66,117.67,62.98,39.58,32.25,26.22,25.68,
17.69,16.62；HRMS:m/z(ESI)[M+Na]+Theoretical value 297.1579, measured value 297.1575.
As Figure 4-Figure 6,5- methylpyrazine-2- formic acid-β-ionol esters: colourless oil liquid.1H NMR
(400MHz,CDCl3) δ ppm 9.17 (s, 1H), 8.59 (s, 1H), 6.26 (d, J=15.79Hz, 1H), 5.80-5.67 (m,
1H),5.64-5.49(m,1H),2.66(s,3H),1.96(s,2H),1.65(s,3H),1.63-1.52(m,5H),1.47-
1.38 (m, 2H), 0.97 (d, J=10.00Hz, 6H)；13C NMR(400MHz,CDCl3)δppm 163.45,157.42,
145.24,144.25,141.13,136.34,132.03,131.29,129.42,73.89,39.31,33.85,32.63,
28.63,21.88,21.30,20.68,19.16；[M+Na]+found 337.1889(calcd.337.1892).
It is analyzed from spectrum elucidation, in conjunction with infrared spectroscopy (IR), high resolution mass spec (1HR-MS) and carbon-13 nmr spectra
(13C-NMR) can determine that gained compound is 5- methylpyrazine -2- formic acid spiceleaf alcohol ester and 5- methylpyrazine -2- formic acid-β -
Ionol esters.
(2) flavoring research of the target product in tobacco
With 95% ethanol as solvent, by target product 5- methylpyrazine -2- formic acid spiceleaf alcohol ester and 5- methylpyrazine -2- first
Acid-β-ionol esters are made into the solution of mass fraction 1% respectively.It takes on 0.5g, 1.0g, 5.0g, 10.0g and 15.0g respectively
The solution containing target product is stated, then uniformly spray is added in the 100g blank cigarette shreds of five parts of non-flavoring and casings, is rolled, is respectively chosen
100 same weight cigarette are selected, 22 DEG C ± 1 DEG C of temperature is placed in, balances 48h in the climatic chamber of humidity 60% ± 2%, comment
It inhales.Control sample is blank cigarette, and control sample equally balances 48h under the conditions of identical epidemic disaster.
1 5- methylpyrazine -2- formic acid-β of table-ionol esters flavoring smoking result
The flavoring smoking result of 2 5- methylpyrazine -2- formic acid spiceleaf alcohol ester of table
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Belong to those skilled in the art in the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of, all answers
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be subject to the protection scope in claims.
Claims (4)
1. a kind of cigarette preparation method of latent fragrant monomer 5- methylpyrazine -2- formate ester, it is characterised in that: including walking as follows
It is rapid:
It takes 5- methylpyrazine -2- formic acid and single hydroxyl alcohol to be dissolved in dry methylene chloride, stirs one section of 10min-30min, add
Enter 4-dimethylaminopyridine (DMAP) and 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl), room
Temperature stirring 4-12h, TLC monitoring reaction, tracks reaction end, into organic phase plus water washing, liquid separation, then it is molten with saturated sodium-chloride
Liquid washing, liquid separation, organic phase anhydrous Na2SO4It is dry, it is concentrated to give crude product, column chromatography for separation is then carried out and is used up to the cigarette
Latent perfume monomer 5- methylpyrazine -2- formate ester；The single hydroxyl alcohol is geraniol or ionol, when single hydroxyl alcohol is perfume
When leaf-alcohol, obtained product is 5- methylpyrazine -2- formic acid spiceleaf alcohol ester, when single hydroxyl alcohol is ionol, obtained production
Object is 5- methylpyrazine -2- formic acid-β-ionol esters, and the two structural formula is as follows:
2. the cigarette as described in claim 1 preparation method of latent fragrant monomer 5- methylpyrazine -2- formate ester, feature exist
In: the column chromatography for separation eluent is the mixing of ethyl acetate and petroleum ether, the volume ratio 100:1-20:1 of the two.
3. the cigarette as described in claim 1 preparation method of latent fragrant monomer 5- methylpyrazine -2- formate ester, feature exist
In: the molar ratio of the 5- methylpyrazine -2- formic acid and single hydroxyl alcohol is between 0.9:1-1:0.9.
4. such as the latent fragrant monomer 5- methylpyrazine -2- formate ester of cigarette of any one of claim 1-3 the method preparation
As application of the fragrance-enhancing tobacco agent in cigarette, it is applied in cigarette as fragrance-enhancing tobacco agent, additive amount is pipe tobacco weight
0.01-0.05%.
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| US5172706A (en) * | 1992-01-21 | 1992-12-22 | Philip Morris Incorporated | Smoking compositions containing an oxalate flavorant-release additive |
| CN101686719A (en) * | 2007-07-25 | 2010-03-31 | 菲利普莫里斯生产公司 | The method of the spices of polycarboxylic flavorant ester salt and release hydroxyl |
| CN102304154A (en) * | 2011-09-05 | 2012-01-04 | 川渝中烟工业公司 | Monosaccharide alpha-ionol carbonic acid monoester compounds and preparation method and use thereof |
| CN102311465A (en) * | 2011-09-05 | 2012-01-11 | 川渝中烟工业公司 | Monosaccharide geraniol carbonate monoester compound and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5172706A (en) * | 1992-01-21 | 1992-12-22 | Philip Morris Incorporated | Smoking compositions containing an oxalate flavorant-release additive |
| CN101686719A (en) * | 2007-07-25 | 2010-03-31 | 菲利普莫里斯生产公司 | The method of the spices of polycarboxylic flavorant ester salt and release hydroxyl |
| CN102304154A (en) * | 2011-09-05 | 2012-01-04 | 川渝中烟工业公司 | Monosaccharide alpha-ionol carbonic acid monoester compounds and preparation method and use thereof |
| CN102311465A (en) * | 2011-09-05 | 2012-01-11 | 川渝中烟工业公司 | Monosaccharide geraniol carbonate monoester compound and preparation method and application thereof |
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