CN106496149A - Preparation method and applications of the cigarette with latent 2 formate ester of perfume monomer pyrazine - Google Patents
Preparation method and applications of the cigarette with latent 2 formate ester of perfume monomer pyrazine Download PDFInfo
- Publication number
- CN106496149A CN106496149A CN201610881051.9A CN201610881051A CN106496149A CN 106496149 A CN106496149 A CN 106496149A CN 201610881051 A CN201610881051 A CN 201610881051A CN 106496149 A CN106496149 A CN 106496149A
- Authority
- CN
- China
- Prior art keywords
- pyrazine
- cigarette
- formic acid
- ionol
- esters
- 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
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 235000019504 cigarettes Nutrition 0.000 title claims abstract description 39
- -1 formate ester Chemical class 0.000 title claims abstract description 22
- 239000000178 monomer Substances 0.000 title claims abstract description 21
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000002304 perfume Substances 0.000 title claims abstract description 20
- 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
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims abstract description 15
- 208000035126 Facies Diseases 0.000 claims abstract description 14
- 241000208125 Nicotiana Species 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 14
- 239000012043 crude product Substances 0.000 claims abstract description 11
- 239000005792 Geraniol Substances 0.000 claims abstract description 10
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 claims abstract description 10
- 229940113087 geraniol Drugs 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- CNOPDZWOYFOHGN-BQYQJAHWSA-N Beta-Ionol Chemical compound CC(O)\C=C\C1=C(C)CCCC1(C)C CNOPDZWOYFOHGN-BQYQJAHWSA-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
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- CNOPDZWOYFOHGN-UHFFFAOYSA-N beta-ionol Natural products CC(O)C=CC1=C(C)CCCC1(C)C CNOPDZWOYFOHGN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000012544 monitoring process Methods 0.000 claims abstract description 7
- 150000003839 salts Chemical class 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
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000004440 column chromatography Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 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
- NIPZZXUFJPQHNH-UHFFFAOYSA-N pyrazine-2-carboxylic acid Chemical class OC(=O)C1=CN=CC=N1 NIPZZXUFJPQHNH-UHFFFAOYSA-N 0.000 claims description 35
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 10
- 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 2
- 238000000034 method Methods 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 1
- 239000000779 smoke Substances 0.000 abstract description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract 6
- 235000019253 formic acid Nutrition 0.000 abstract 3
- 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 2
- 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
- 150000001298 alcohols Chemical class 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 5
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 235000019634 flavors Nutrition 0.000 description 4
- 238000002156 mixing Methods 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
- 238000001035 drying Methods 0.000 description 3
- 239000000463 material Substances 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
- 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
- 230000009189 diving Effects 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 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
- 235000013599 spices Nutrition 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
- WBOHXLDSPBIPTP-UHFFFAOYSA-N N,N-dimethyl-1,8-naphthyridin-4-amine Chemical compound CN(C1=CC=NC2=NC=CC=C12)C WBOHXLDSPBIPTP-UHFFFAOYSA-N 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 238000013459 approach Methods 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
- 150000002148 esters Chemical class 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
- 238000011160 research 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
- 238000012360 testing method 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
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/44—Benzopyrazines 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 carbon atoms of the hetero ring
-
- 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 latent 2 formate ester of perfume monomer pyrazine, comprises the steps：Take 2 formic acid of pyrazine and β ionols are dissolved in dry dichloromethane, stirring 10min 30min, add 4 dimethylamino naphthyridines and 1 ethyl (3 dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate, 4 12h are stirred at room temperature, TLC monitoring reactions, track reaction end.Add water in organic faciess washing, point liquid, then is washed with saturated nacl aqueous solution, point liquid, organic faciess anhydrous Na2SO4Dry, be concentrated to give crude product, column chromatography for separation obtains final product the product.The present invention prepares 2 formic acid Herba Pelargonii Graveolentiss alcohol ester of pyrazine and 2 formic acid β ionol esters of pyrazine compared with geraniol and β ionol parent things, the addition in Medicated cigarette can significantly be improved, it is applied in Medicated cigarette as fragrance-enhancing tobacco agent, zest and the miscellaneous QI of Medicated cigarette can be reduced, the mellow and full sense of cigarette smoke and comfortableness is improved.
Description
Technical field
The present invention relates to essence and flavoring agent and tobacco manufacture field, specifically a kind of cigarette perfume monomer pyrazine -2- formic acid esters of diving
The preparation method and applications of class.
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 pyrazine -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 is with latent perfume monomer pyrazine -2- formic acid
The preparation method of esters and its application in Medicated cigarette.
For achieving the above object, the present invention is adopted the following technical scheme that：
Cigarette is as follows with the structural formula of monomer perfume pyrazine -2- formic acid esters：
A kind of preparation method of cigarette with monomer perfume pyrazine -2- formic acid esters, which comprises the steps：
Take pyrazine -2- formic acid and β-ionol is dissolved in dry dichloromethane, stir 10min-30min, add 4-
Dimethylamino naphthyridine (DMAP) and 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl), room temperature is stirred
4-12h is mixed, TLC monitoring reactions track reaction end.Add water in organic faciess washing, point liquid, then is washed with saturated nacl aqueous solution
Wash, point liquid, organic faciess anhydrous Na2SO4Dry, be concentrated to give crude product, column chromatography for separation obtains final product the cigarette monomer perfume pyrrole
Piperazine -2- formic acid esters.
Further, described column chromatography for separation eluent is ethyl acetate and petroleum ether, and both volume ratios are 100:
1-20:1.
Further, the molar ratio of described pyrazine -2- formic acid and single hydroxyl alcohol is 0.9:1-1:Between 0.9.
Further, described single hydroxyl alcohol is geraniol or ionol, when single hydroxyl alcohol is geraniol, obtains
Product is pyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters；When single hydroxyl alcohol is ionol, the product for obtaining is pyrazine -2- formic acid-β-purple
Rowland alcohol ester, both structural formulas are as follows：
Further, the kind cigarette that prepared by method as defined above is with monomer perfume pyrazine -2- formic acid esters as fragrance-enhancing tobacco agent
Application in Medicated cigarette, is applied in Medicated cigarette as fragrance-enhancing tobacco agent, 0.01-0.05% of the addition for tobacco shred weight.
The compounds of this invention pyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters and pyrazine -2- formic acid-β-ionol esters are a kind of latent sweetening treatment
Compound, under room temperature, which is stable in properties, is colourless liquid, but which passes through to heat cleavable and produces tool and be significantly increased tobacco aroma thing
Matter.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 prepare pyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters and pyrazine -2- formic acid-β-ionol esters compared with geraniol and β -
Ionol parent thing, can significantly improve the addition in Medicated cigarette, and not affect the outer fragrant kind of Medicated cigarette.
2. the present invention with DMAP/1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate is
Pyrazine -2- formic acid and geraniol, β-ionol esterification reaction condensation reagent, can significantly improve reaction yield, locate after simplifying
Science and engineering skill.
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 pyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol ester 1H NMR nuclear magnetic spectrograms；
Fig. 2 is pyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol ester 13C NMR nuclear magnetic spectrograms；
Fig. 3 is pyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol ester HRMS high-resolution spectrograms；
Fig. 4 is pyrazine -2- formic acid-β-ionol esters 1H NMR nuclear magnetic spectrograms；
Fig. 5 is pyrazine -2- formic acid-β-ionol esters 13C NMR nuclear magnetic spectrograms；
Fig. 6 is pyrazine -2- formic acid-β-ionol esters 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 pyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters：
Take 10mmol geraniol and 10mmol pyrazine -2- formic acid is dissolved in the dichloromethane of 100ml dryings, stir 10min
Afterwards, DMAP (DMAP) is added (5mmol) and 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate
(EDCHCl) (11mmol), it is stirred at room temperature, TLC monitoring reaction (petroleum ether：Ethyl acetate=10:1, Rf=0.5, ultraviolet 254nm
Colour developing), track reaction end.The 50mL that adds water in organic faciess is washed, point liquid, then is 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 100-200 mesh
Silica gel 4g, decompression be spin-dried for mixing sample, use petroleum ether in the silica gel column chromatography strain with 80g 100-200 mesh：Ethyl acetate=60:1 is slow
Slow eluting, obtains target product after concentration, drying.
Embodiment two
The preparation method of tobacco aromatics using monomer pyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters：
Take 10mmol geraniol and 10.5mmol pyrazine -2- formic acid is dissolved in the dichloromethane of 100ml dryings, stirring
After 10min, add DMAP (DMAP) (4mmol) and 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimine
Hydrochlorate (EDCHCl) (11 mmol), is stirred at room temperature, TLC monitoring reaction (petroleum ether：Ethyl acetate=10:1, Rf=0.5, purple
Outer 254nm colour developings), track reaction end.The 50mL that adds water in organic faciess is washed, point liquid, then uses 50mL saturated nacl aqueous solutions
Washing, 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, decompression are spin-dried for mixing sample, use petroleum ether in the silica gel column chromatography strain with 80g 100-200 mesh：Ethyl acetate
=60:1 slowly eluting, concentration, dry after obtain target product.
Embodiment three
The preparation method of tobacco aromatics using monomer pyrazine -2- formic acid-β-ionol esters：
In there-necked flask, add the 20mmol β-ionol for weighing and 20mmol pyrazine -2- formic acid to be dissolved in 200ml and do
In dry dichloromethane, after stirring 10min, add DMAP (DMAP) (9mmol) and 1- ethyls-(3- dimethyl
Aminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDC HCl) (22mmol), under room temperature stir, TLC monitoring reaction (petroleum ether：Second
Acetoacetic ester=10:1, Rf=0.5, ultraviolet 254nm colour developings), tracking reaction is to terminal.To in organic faciess, add pure water 100mL to wash
Wash, point liquid, 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 the silica gel 7g of 100-200 mesh, and decompression is spin-dried for mixing sample, with 100g 100-200 mesh
Silica gel column chromatography post separation, eluant petroleum ether：Ethyl acetate=80:1 slowly eluting, concentration, dry after obtain target product
Thing
Example IV
The preparation method of tobacco aromatics using monomer pyrazine -2- formic acid-β-ionol esters：
In there-necked flask, add the 20mmol β-ionol for weighing and 21mmol pyrazine -2- formic acid to be dissolved in 200ml and do
In dry dichloromethane, after stirring 10min, add DMAP (DMAP) (8mmol) and 1- ethyls-(3- dimethyl
Aminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDC HCl) (22mmol), under room temperature stir, TLC monitoring reaction (petroleum ether：Second
Acetoacetic ester=10:1, Rf=0.5, ultraviolet 254nm colour developings), tracking reaction is to terminal.To in organic faciess, add pure water 100mL to wash
Wash, point liquid, 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 the silica gel 7g of 100-200 mesh, and decompression is spin-dried for mixing sample, with 100g 100-200 mesh
Silica gel column chromatography post separation, eluant petroleum ether：Ethyl acetate=80:1 slowly eluting, concentration, dry after obtain target product
Thing
(1) structural characterization of target product
By red high resolution mass spectrum (HR-MS), carbon-13 nmr spectra (1H-NMR 13C-NMR) respectively to embodiment gained
Target product pyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters and pyrazine -2- formic acid-β-ionol esters carry out structural characterization, and concrete data are such as
Under：
Pyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters：Colourless oil liquid.1H NMR(400MHz,CDCl3)δppm 9.32(s,1H),
8.75 (d, J=11.07Hz, 2H), 5.52 (t, J=6.02,6.02Hz, 1H), 5.11 (d, J=17.08Hz, 1H), 4.96
(dd, J=14.72,7.24Hz, 2H), 2.24-2.04 (m, 4H), 1.79 (s, 3H), 1.67 (s, 3H), 1.60 (s, 3H)；13C
NMR(400MHz,CDCl3δppm 163.94,147.55,146.30,144.40,143.69,131.90,123.64,118.41,
117.520,63.19,39.58,26.23,25.67,17.69,16.62；HRMS:m/z(ESI)[M+Na]+Theoretical value
283.1422, measured value 283.1414.
Pyrazine -2- formic acid-β-ionol esters：Colourless oil liquid.1H NMR(400MHz,CDCl3)δppm 9.31(s,
1H), 8.75 (s, 2H), 6.28 (d, J=15.84Hz, 1H), 5.80-5.71 (m, 1H), 5.58 (dd, J=15.89,7.36Hz,
1H), 1.97 (t, J=5.93,5.93Hz, 2H), 1.66 (s, 3H), 1.58 (dd, J=12.82,4.97Hz, 6H), 1.44 (dd,
J=5.60,3.89Hz, 2H), 1.00 (s, 3H), 0.97 (s, 3H)；13C NMR(400MHz,CDCl3)δppm 163.20,
147.43,146.21,144.46,143.97,136.30,131.85,131.565,129.55,74.33,39.31,33.88,
32.66,28.67,28.65,21.35,20.71,19.17；HRMS：[M+Na]+found 323.1735
(calcd.323.1735).
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 is pyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters and pyrazine -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 pyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters and pyrazine -2- formic acid-β-violet
Alcohol ester is made into the solution of mass fraction 1% respectively.It is above-mentioned containing target product that 0.5g, 1.0g, 5.0g, 10.0g and 15.0g are taken respectively
Solution, then uniform spray is added in the 100g blank cigarette shreds of seven parts of non-flavoring and casings, rolls, respectively pick out 100 with
One weight Medicated cigarette, is placed in 22 DEG C ± 1 DEG C of temperature, balances 48h, smoke panel test in the climatic chamber of humidity 60% ± 2%.Control sample is
Blank Medicated cigarette, control sample balance 48h equally under the conditions of identical epidemic disaster.
The perfuming smoking result of 1 pyrazine -2- formic acid Herba Pelargonii Graveolentiss alcohol esters of table
The perfuming smoking result of 2 pyrazine -2- formic acid-β of table-ionol esters
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 pyrazine -2- formate esters, it is characterised in that comprise the steps：Take pyrrole
Piperazine -2- formic acid and β-ionol are dissolved in dry dichloromethane, stir 10min-30min, add DMAP
With 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate, 4-12h is stirred at room temperature, TLC monitoring reactions, tracking are anti-
Answer terminal.Add water in organic faciess washing, point liquid, then is washed with saturated nacl aqueous solution, point liquid, organic faciess anhydrous Na2SO4
Dry, be concentrated to give crude product, column chromatography for separation obtains final product the cigarette monomer perfume pyrazine -2- formic acid esters.
2. the preparation method of cigarette as claimed in claim 1 with latent perfume monomer pyrazine -2- formate esters, it is characterised in that：Described
Column chromatography for separation eluent be ethyl acetate and petroleum ether, both volume ratios are 100:1-20:1.
3. the preparation method of cigarette as claimed in claim 1 with latent perfume monomer pyrazine -2- formate esters, it is characterised in that：Described
Pyrazine -2- formic acid and single hydroxyl alcohol molar ratio 0.9:1-1:Between 0.9.
4. the preparation method of cigarette as claimed in claim 1 with latent perfume monomer pyrazine -2- formate esters, it is characterised in that：Described
Single hydroxyl alcohol be geraniol or ionol, when single hydroxyl alcohol is geraniol, the product for obtaining is pyrazine -2- formic acid Herba Pelargonii Graveolentiss
Alcohol ester；When single hydroxyl alcohol is ionol, the product for obtaining is pyrazine -2- formic acid-β-ionol esters, and both structural formulas are such as
Under：
5. the cigarette that prepared by a kind of method as any one of claim 1-4 is made with latent perfume monomer pyrazine -2- formate esters
For 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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| CN107417679A (en) * | 2017-08-04 | 2017-12-01 | 河南农业大学 | 1,3 azoles substitute the preparation method of pyrazine compounds |
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