CN106496147A - Preparation method and applications of the cigarette with 5 methylpyrazine of latent perfume monomer, 2 formate ester - Google Patents
Preparation method and applications of the cigarette with 5 methylpyrazine of latent perfume monomer, 2 formate ester Download PDFInfo
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- CN106496147A CN106496147A CN201610880105.XA CN201610880105A CN106496147A CN 106496147 A CN106496147 A CN 106496147A CN 201610880105 A CN201610880105 A CN 201610880105A CN 106496147 A CN106496147 A CN 106496147A
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- Prior art keywords
- methylpyrazine
- cigarette
- formic acid
- preparation
- product
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- Granted
Links
- 235000019504 cigarettes Nutrition 0.000 title claims abstract description 39
- -1 formate ester Chemical class 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 title claims abstract description 20
- 239000002304 perfume Substances 0.000 title claims abstract description 20
- CAWHJQAVHZEVTJ-UHFFFAOYSA-N methylpyrazine Chemical compound CC1=CN=CC=N1 CAWHJQAVHZEVTJ-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 16
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 208000035126 Facies Diseases 0.000 claims abstract description 14
- 241000208125 Nicotiana Species 0.000 claims abstract description 13
- 239000012043 crude product Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 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
- 238000000926 separation method Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004440 column chromatography Methods 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000007832 Na2SO4 Substances 0.000 claims abstract description 3
- 239000012467 final product Substances 0.000 claims abstract description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 3
- RBYJWCRKFLGNDB-UHFFFAOYSA-N 5-methylpyrazine-2-carboxylic acid Chemical class CC1=CN=C(C(O)=O)C=N1 RBYJWCRKFLGNDB-UHFFFAOYSA-N 0.000 claims description 30
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 26
- 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 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 13
- 150000001298 alcohols Chemical class 0.000 claims description 10
- 239000005792 Geraniol Substances 0.000 claims description 9
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 claims description 9
- 229940113087 geraniol Drugs 0.000 claims description 9
- 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
- TVCXVUHHCUYLGX-UHFFFAOYSA-N 2-Methylpyrrole Chemical class CC1=CC=CN1 TVCXVUHHCUYLGX-UHFFFAOYSA-N 0.000 claims description 2
- 230000009189 diving Effects 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- JSSXHAMIXJGYCS-UHFFFAOYSA-N piperazin-4-ium-2-carboxylate Chemical compound OC(=O)C1CNCCN1 JSSXHAMIXJGYCS-UHFFFAOYSA-N 0.000 claims 1
- 235000002639 sodium chloride Nutrition 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 abstract description 6
- 239000000779 smoke Substances 0.000 abstract description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract 1
- DXRFZHILMCWCNG-UHFFFAOYSA-N N,N-dimethyl-1,8-naphthyridin-2-amine Chemical class C1=CC=NC2=NC(N(C)C)=CC=C21 DXRFZHILMCWCNG-UHFFFAOYSA-N 0.000 abstract 1
- 235000019253 formic acid Nutrition 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000796 flavoring agent Substances 0.000 description 5
- 239000003205 fragrance 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
- 235000019634 flavors Nutrition 0.000 description 4
- 239000000463 material Substances 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
- 235000013599 spices Nutrition 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 244000061176 Nicotiana tabacum Species 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000000391 smoking effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-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
- 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
- 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
- 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
- 230000000694 effects Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 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
- 239000007921 spray Substances 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
Abstract
A kind of cigarette preparation method of 5 methylpyrazine of latent perfume monomer, 2 formate ester, comprises the steps：Take 5 methylpyrazine, 2 formic acid and single hydroxyl alcohol is dissolved in dry dichloromethane, one section of 10min 30min of stirring, 4 dimethylamino naphthyridines (DMAP) and 1 ethyl (3 dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl) is added, 4 12h, TLC monitoring reactions is stirred at room temperature, tracking reaction end, add water in organic faciess washing, point liquid, then is washed with saturated nacl aqueous solution, divide liquid, organic faciess anhydrous Na2SO4Dry, be concentrated to give crude product, then carry out column chromatography for separation and obtain final product the product.Product prepared by the present invention can significantly improve the addition in Medicated cigarette, and not affect the outer fragrant kind of Medicated cigarette, be applied in Medicated cigarette as fragrance-enhancing tobacco agent, it is possible to decrease the zest of Medicated cigarette and miscellaneous QI, improve the mellow and full sense of cigarette smoke and comfortableness.
Description
Technical field
The present invention relates to essence and flavoring agent and tobacco manufacture field, specifically a kind of cigarette perfume monomer 5- methylpyrazine -2- that dive
The preparation method and applications of formate ester.
Background technology
Many excellent spice are as its high high-temp stability is poor, volatility compared with strong, fragrance remaining time is short the problems such as limit
Which is widely applied.Latent Studies of The Aromatic Substances is that a class relative molecular mass is big, the material that boiling point is higher, and fragrance is less or does not have perfume (or spice) in itself
Gas, but can discharge with fragrance fragrance through the approach such as chemical hydrolysis, enzymolysis or microbial action, pyrolysis, photodestruciton
Compound.Because of its safety preferably, listed in natural perfume material category in the world, allocated some local flavor edible essence effects with which
Very well.Different from volatility and half volatile fragrance matter, perfume class compound of diving is reducing artificial flavor and taste compensation vestige
It is not result in the significant changes of the material delivering amount such as nicotine in cigarette mainstream flue gas, tar simultaneously, more longlasting can stably provides cigarette
Gas characteristic chicken flavor.In prior art, latent Studies of The Aromatic Substances is widely applied in the adding technology of cigarette shreds, and the present invention provides one
Preparation method of the cigarette with latent perfume monomer 5- methylpyrazine -2- formate esters is planted, and inquires into its application in perfuming cigarette.
Content of the invention
The present invention is in order to develop new cigarette flavor precursors, there is provided a kind of new cigarette with latent perfume monomer 5- methylpyrazines-
The preparation method of 2- formate esters and its application in Medicated cigarette.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of cigarette preparation method of monomer perfume 5- methylpyrazine -2- formic acid esters, comprises the steps：
Take 5- methylpyrazine -2- formic acid and single hydroxyl alcohol is dissolved in dry dichloromethane, stir one section of 10min-
30min, adds DMAP (DMAP) and 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate
(EDCHCl), 4-12h, TLC monitoring reaction (petroleum ether are stirred at room temperature：Ethyl acetate=10:1, Rf=0.5, ultraviolet 254nm show
Color), track reaction end.Add water in organic faciess washing, point liquid, then is washed with saturated nacl aqueous solution, and point liquid, organic faciess are used
Anhydrous Na2SO4Dry, be concentrated to give crude product, column chromatography is analyzed, then carry out column chromatography for separation and the cigarette is obtained final product with latent perfume monomer
5- methylpyrazine -2- formate esters.
Further, described column chromatography for separation eluent is ethyl acetate and petroleum ether, both volume ratios 100:1-
20:1.
Further, the molar ratio of described 5- methylpyrazine -2- formic acid and single hydroxyl alcohol is 0.9:1-1:0.9 it
Between.
Further, described single hydroxyl alcohol is geraniol or ionol, when single hydroxyl alcohol is geraniol, obtains
Product is 5- methylpyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters, and when single hydroxyl alcohol is ionol, the product for obtaining is 5- methyl pyrroles
Piperazine -2- formic acid-β-ionol esters, both structural formulas are as follows：
Further, the cigarette that prepared by method as defined above is with monomer perfume 5- methylpyrazine -2- formate esters as Nicotiana tabacum L.
Application of the fumet in Medicated cigarette, is applied in Medicated cigarette as fragrance-enhancing tobacco agent, 0.01- of the addition for tobacco shred weight
0.05%.
The compounds of this invention 5- methylpyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters and 5- methylpyrazine -2- formic acid-β-ionol esters
For a kind of latent aroma compounds, under room temperature, which is stable in properties, is colourless liquid, but which passes through to heat cleavable and produce that there is substantially increasing
Plus tobacco aroma material.Such as 3- oxo-beta-ionones, geraniol, pyrazine, monoterpene vinyl compound.
Compared to the prior art, beneficial effects of the present invention：
1. the present invention prepares 5- methylpyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters and 5- methylpyrazine -2- formic acid-β-ionol esters
Compared with geraniol and β-ionol parent thing, the addition in Medicated cigarette can be significantly improved, and does not affect the outer perfume (or spice) of Medicated cigarette
Kind.
2. the present invention with DMAP/1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate is
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 is developed, are applied in Medicated cigarette as fragrance-enhancing tobacco agent first,
Zest and the miscellaneous QI of Medicated cigarette can be reduced, the mellow and full sense of cigarette smoke and comfortableness is improved.
Description of the drawings
Fig. 1 is 5- methylpyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol ester 1H NMR nuclear magnetic spectrograms；
Fig. 2 is 5- methylpyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol ester 13C NMR nuclear magnetic spectrograms；
Fig. 3 is 5- methylpyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol ester HRMS high-resolution spectrograms；
Fig. 4 is 5- methylpyrazine -2- formic acid-β-ionol 1H NMR nuclear magnetic spectrograms；
Fig. 5 is 5- methylpyrazine -2- formic acid-β-ionol 13C NMR nuclear magnetic spectrograms；
Fig. 6 is 5- methylpyrazine -2- formic acid-β-ionol HRMS high-resolution spectrograms.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, is easy to be well understood to the interior of the present invention
Hold, but they do not constitute to the present invention and limit.
Embodiment one
The preparation method of tobacco aromatics using monomer 5- methylpyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters：
Take 10mmol geraniol and 10mmol5- methylpyrazine -2- formic acid is dissolved in the dichloromethane of 100ml dryings, stirring
After 10min, add DMAP (DMAP) (5mmol) and 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimine
Hydrochlorate (EDCHCl) (11mmol), is stirred at room temperature, TLC monitoring reactions, tracks reaction end.The 50mL that adds water in organic faciess is washed
Wash, point liquid, then washed with 50mL saturated nacl aqueous solutions, point liquid, organic faciess are dried with anhydrous Na 2SO4, are concentrated to give crude product.
Crude product 50mL dichloromethane dissolves, and adds the silica gel 4g of 100-200 mesh, and decompression is spin-dried for mixing sample, with 80g 100-200 purposes
Petroleum ether is used in silica gel column chromatography strain：Ethyl acetate=60:1 slowly eluting, concentration, dry after obtain target product.
Embodiment two
The preparation method of tobacco aromatics using monomer 5- methylpyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters：
Take 10mmol geraniol and 1.05mmol5- methylpyrazine -2- formic acid is dissolved in the dichloromethane of 100ml dryings, stir
After mixing 10min, add DMAP (DMAP) (4mmol) and 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne two is sub-
Amine hydrochlorate (EDCHCl) (11mmol), is stirred at room temperature, TLC monitoring reactions, tracks reaction end.Add water in organic faciess 50mL
Washing, point liquid, then washed with 50mL saturated nacl aqueous solutions, point liquid, organic faciess are dried with anhydrous Na 2SO4, are concentrated to give thick product
Thing.Crude product 50mL dichloromethane dissolves, and adds the silica gel 4g of 100-200 mesh, decompression to be spin-dried for mixing sample, uses 80g 100-200
Petroleum ether is used in purpose silica gel column chromatography strain：Ethyl acetate=60:1 slowly eluting, concentration, dry after obtain target product.
Embodiment three
The preparation method of tobacco aromatics using monomer 5- methylpyrazine -2- formic acid-β-ionol esters：
In there-necked flask, the 20mmol β-ionol for weighing and 10mmol 5- methylpyrazine -2- formic acid is added to be dissolved in
In the dichloromethane that 200ml is dried, after stirring 10min, add DMAP (DMAP) (10mmol) and 1- ethyls-
(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate (EDC HCl) (22mmol), is stirred under room temperature, TLC monitoring reactions,
Tracking reaction is to terminal.Add pure water 100mL washings, point liquid in organic faciess, then washed with 100mL saturated nacl aqueous solutions,
Liquid, organic faciess is divided to be dried with anhydrous Na 2SO4, the crude product of concentration.Crude product 10mL dichloromethane dissolves, and adds 100-200
Purpose silica gel 7g, decompression are spin-dried for mixing sample, with the silica gel column chromatography post separation of 100g 100-200 mesh, eluant petroleum ether：Acetic acid
Ethyl ester=80:1 slowly eluting, concentration, dry after obtain target product
Example IV
The preparation method of tobacco aromatics using monomer 5- methylpyrazine -2- formic acid-β-ionol esters：
In there-necked flask, the 20mmol β-ionol for weighing and 21mmol 5- methylpyrazine -2- formic acid is added to be dissolved in
In the dichloromethane that 200ml is dried, after stirring 10min, add DMAP (DMAP) (8mmol) and 1- ethyls-(3-
Dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDC HCl) (22mmol), under room temperature stir, TLC monitoring reaction, tracking
Reaction is to terminal.Add pure water 100mL washings, point liquid in organic faciess, then washed with 100mL saturated nacl aqueous solutions, point liquid,
Organic faciess are dried with anhydrous Na 2SO4, the crude product of concentration.Crude product 10mL dichloromethane dissolves, and adds 100-200 purposes
Silica gel 7g, decompression are spin-dried for mixing sample, with the silica gel column chromatography post separation of 100g 100-200 mesh, eluant petroleum ether：Ethyl acetate
=80:1 slowly eluting, concentration, dry after obtain target product
(1) structural characterization of target product
By red high resolution mass spectrum (HR-MS), carbon-13 nmr spectra (1H-NMR13C-NMR) respectively to embodiment gained mesh
Mark product 5- methylpyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters and 5- methylpyrazine -2- formic acid-β-ionol esters carry out structural characterization,
Concrete data are as follows：
As Figure 1-3,5- methylpyrazines -2- geranyl formates：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- methylpyrazines-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).
Analyze from spectrum elucidation, in conjunction with infrared spectrum (IR), high resolution mass spec (1HR-MS) and carbon-13 nmr spectra
(13C-NMR) can determine that gained compound be 5- methylpyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters and 5- methylpyrazine -2- formic acid-β -
Ionol esters.
(2) perfuming research of the target product in Nicotiana tabacum L.
With 95% ethanol as solvent, by target product 5- methylpyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters and 5- methylpyrazine -2- first
Acid-β-ionol esters are made into the solution of mass fraction 1% respectively.Taken on 0.5g, 1.0g, 5.0g, 10.0g and 15.0g respectively
The solution containing target product is stated, then uniform 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 Medicated cigarette are selected, 22 DEG C ± 1 DEG C of temperature is placed in, and 48h are balanced in the climatic chamber of humidity 60% ± 2%, are commented
Inhale.Control sample is that blank Medicated cigarette, control sample balance 48h equally under the conditions of identical epidemic disaster.
The perfuming smoking result of 1 5- methylpyrazine -2- formic acid-β of table-ionol esters
The perfuming smoking result of 2 5- methylpyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters of table
The above, the only specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, any
Belong to those skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in all are answered
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be defined by scope of the claims.
Claims (5)
1. the preparation method of a kind of cigarette with latent perfume monomer 5- methylpyrazine -2- formate esters, it is characterised in that：Including following step
Suddenly：
Take 5- methylpyrazine -2- formic acid and single hydroxyl alcohol is dissolved in dry dichloromethane, stir one section of 10min-30min, plus
Enter DMAP (DMAP) and 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl), room
Temperature stirring 4-12h, TLC monitoring reaction, tracks reaction end, and add water in organic faciess washing, point liquid, then molten with saturated sodium-chloride
Liquid is washed, point liquid, organic faciess anhydrous Na2SO4Dry, be concentrated to give crude product, then carry out column chromatography for separation and obtain final product the cigarette use
Latent perfume monomer 5- methylpyrazine -2- formate esters.
2. cigarette as claimed in claim 1 uses the preparation method of latent perfume monomer 5- methylpyrazine -2- formate esters, its feature to exist
In：Mixing of the described column chromatography for separation eluent for ethyl acetate and petroleum ether, both volume ratios 100:1-20:1.
3. cigarette as claimed in claim 1 uses the preparation method of latent perfume monomer 5- methylpyrazine -2- formate esters, its feature to exist
In：The molar ratio of described 5- methylpyrazine -2- formic acid and single hydroxyl alcohol is 0.9:1-1:Between 0.9.
4. cigarette as claimed in claim 1 uses the preparation method of latent perfume monomer 5- methylpyrazine -2- formate esters, its feature to exist
In：Described single hydroxyl alcohol is geraniol or ionol, and when single hydroxyl alcohol is geraniol, the product for obtaining is 5- methyl pyrroles
Piperazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters, when single hydroxyl alcohol is ionol, the product for obtaining is 5- methylpyrazine -2- formic acid-β-purple sieve
Blue alcohol ester, both structural formulas are as follows：
5. the cigarette that prepared by method as any one of claim 1-4 perfume monomer 5- methylpyrazine -2- formate esters of diving
As application of the fragrance-enhancing tobacco agent in Medicated cigarette, it is applied in Medicated cigarette as fragrance-enhancing tobacco agent, addition is tobacco shred weight
0.01-0.05%.
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Citations (4)
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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 |
-
2016
- 2016-10-09 CN CN201610880105.XA patent/CN106496147B/en active Active
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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