CN106496112A - Preparation method and applications of the cigarette with latent 3,5 diformic ester of perfume monomer pyridine - Google Patents
Preparation method and applications of the cigarette with latent 3,5 diformic ester of perfume monomer pyridine Download PDFInfo
- Publication number
- CN106496112A CN106496112A CN201610880174.0A CN201610880174A CN106496112A CN 106496112 A CN106496112 A CN 106496112A CN 201610880174 A CN201610880174 A CN 201610880174A CN 106496112 A CN106496112 A CN 106496112A
- Authority
- CN
- China
- Prior art keywords
- pyridine
- cigarette
- dioctyl phthalate
- esters
- latent
- 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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 101
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 235000019504 cigarettes Nutrition 0.000 title claims abstract description 38
- 239000000178 monomer Substances 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
- 150000002148 esters Chemical class 0.000 title claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 33
- -1 hydroxyl alcohol Chemical compound 0.000 claims abstract description 33
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims abstract description 29
- 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 208000035126 Facies Diseases 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
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 claims abstract description 10
- 239000005792 Geraniol Substances 0.000 claims abstract description 10
- 229940113087 geraniol Drugs 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 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
- 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
- 239000007832 Na2SO4 Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000004440 column chromatography Methods 0.000 claims abstract description 5
- 239000012467 final product Substances 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims description 14
- 241000208125 Nicotiana Species 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 9
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 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
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical class OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 claims description 2
- 244000061176 Nicotiana tabacum Species 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 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 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- CNOPDZWOYFOHGN-BQYQJAHWSA-N Beta-Ionol Chemical class CC(O)\C=C\C1=C(C)CCCC1(C)C CNOPDZWOYFOHGN-BQYQJAHWSA-N 0.000 abstract description 6
- CNOPDZWOYFOHGN-UHFFFAOYSA-N beta-ionol Natural products CC(O)C=CC1=C(C)CCCC1(C)C CNOPDZWOYFOHGN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000779 smoke Substances 0.000 abstract description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 abstract 3
- 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
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 22
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 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
- 239000000463 material Substances 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
- 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
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-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
- 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012512 characterization method 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
- 230000009189 diving Effects 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
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid 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
- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical compound C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 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
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
Abstract
A kind of cigarette preparation method of latent 3,5 diformic ester of perfume monomer pyridine, comprises the steps：Take pyridine 3,5 dioctyl phthalate and single hydroxyl alcohol are dissolved in dry dichloromethane, stir 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, and add water in organic faciess washing, divide liquid, washed with saturated nacl aqueous solution again, point liquid, organic faciess anhydrous Na2SO4Dry, be concentrated to give crude product, column chromatography for separation obtains final product product.The present invention prepares pyridine 3,5 dioctyl phthalate, two Herba Pelargonii Graveolentiss alcohol ester and pyridine 3,5 dioctyl phthalate, two β ionol esters are compared with geraniol and β ionol parent things, it is remarkably improved the addition in Medicated cigarette, it is applied in Medicated cigarette, 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 latent perfume monomer pyridine -3,5- diformazans
The preparation method and applications of esters of gallic acid.
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
Cigarette latent perfume monomer pyridine -3, the preparation method of 5- diformic 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 latent perfume monomer pyridine -3,5- bis-
The preparation method of formate ester 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 monomer perfume pyridine -3, the preparation method of 5- dicarboxylic acid esters, which comprises the steps：Which includes as follows
Step：
Pyridine -3 are taken, 5- dioctyl phthalate and single hydroxyl alcohol are dissolved in dry dichloromethane, stir 10min-30min, added
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 uses saturated nacl aqueous solution
Washing, point liquid, organic faciess anhydrous Na2SO4Dry, be concentrated to give crude product, column chromatography for separation obtains final product the cigarette with latent perfume monomer pyrrole
Pyridine -3,5- diformic esters.
Further, described column chromatography for separation eluent is ethyl acetate and petroleum ether, both volume ratios 100:1-
20:1.
Further, described pyridine -3, the molar ratio of 5- dioctyl phthalate 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 be pyridine -3, two Herba Pelargonii Graveolentiss alcohol ester of 5- dioctyl phthalate, when single hydroxyl alcohol be ionol when, the product for obtaining be pyridine -3,5-
Two-β of dioctyl phthalate-ionol esters, both structural formulas are as follows：
3,5- cinchomeronic acid, two Herba Pelargonii Graveolentiss alcohol ester
3,5- cinchomeronic acid, two-β-ionol esters.
A kind of latent perfume monomer benzenpropanoic acid esters of cigarette prepared by method as defined above are as fragrance-enhancing tobacco agent in Medicated cigarette
Application, is applied in Medicated cigarette as fragrance-enhancing tobacco agent, 0.005-0.05% of the addition for tobacco shred weight.
Two Herba Pelargonii Graveolentiss alcohol ester of the compounds of this invention pyridine -3,5- dioctyl phthalate and two-β of pyridine -3,5- dioctyl phthalate-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, pyridines, monoterpene vinyl compound.
Compared to the prior art, beneficial effects of the present invention：
1. the present invention prepares two Herba Pelargonii Graveolentiss alcohol ester of pyridine -3,5- dioctyl phthalate and pyridine -3,5- dioctyl phthalate two-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
Pyridine -3,5- dioctyl phthalate and geraniol, β-ionol esterification reaction condensation reagent, can significantly improve reaction yield, simplify
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 two Herba Pelargonii Graveolentiss alcohol ester 1H NMR nuclear magnetic spectrograms of pyridine -3,5- dioctyl phthalate；
Fig. 2 is two Herba Pelargonii Graveolentiss alcohol ester 13C NMR nuclear magnetic spectrograms of pyridine -3,5- dioctyl phthalate；
Fig. 3 is two Herba Pelargonii Graveolentiss alcohol ester HRMS high-resolution spectrograms of pyridine -3,5- dioctyl phthalate；
Fig. 4 is two-β of pyridine -3,5- dioctyl phthalate-ionol esters 1H NMR nuclear magnetic spectrograms；
Fig. 5 is two-β of pyridine -3,5- dioctyl phthalate-ionol esters 13C NMR nuclear magnetic spectrograms；
Fig. 6 is two-β of pyridine -3,5- dioctyl phthalate-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 two Herba Pelargonii Graveolentiss alcohol ester of tobacco aromatics using monomer pyridine -3,5- dioctyl phthalate：
10mmol geraniol and 5mmol pyridine -3 are taken, 5- dioctyl phthalate 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 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 anhydrous Na2SO4Dry, be 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 two
The preparation method of two Herba Pelargonii Graveolentiss alcohol ester of tobacco aromatics using monomer pyridine -3,5- dioctyl phthalate：
10mmol geraniol and 5.2mmol pyridine -3 are taken, 5- dioctyl phthalate is dissolved in the dichloromethane of 100ml dryings, stirring
After 10min, add DMAP (DMAP) (4mmol) and 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimine
Hydrochlorate (EDCHCl) (11mmol), 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 anhydrous Na2SO4Dry, be 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 two-β of tobacco aromatics using monomer pyridine -3,5- dioctyl phthalate-ionol esters：
In there-necked flask, the 20mmol β-ionol and 10mmol pyridine -3 for weighing, 5- dioctyl phthalate 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
(petroleum ether：Ethyl acetate=10:1, Rf=0.5, ultraviolet 254nm colour developings), tracking reaction is to terminal.To in organic faciess plus pure
Water 100mL is washed, point liquid, then is washed with 100mL saturated nacl aqueous solutions, point liquid, organic faciess anhydrous Na2SO4Dry, concentration
Crude product.Crude product 10mL dichloromethane dissolves, and adds the silica gel 7g of 100-200 mesh, decompression to be spin-dried for mixing sample, uses 100g
The silica gel column chromatography post separation of 100-200 mesh, eluant petroleum ether：Ethyl acetate=80:1 slowly eluting, concentration, dry after
Arrive target product
Example IV
The preparation method of two-β of tobacco aromatics using monomer pyridine -3,5- dioctyl phthalate-ionol esters：
In there-necked flask, the 20mmol β-ionol and 10.5mmol pyridine -3 for weighing, 5- dioctyl phthalate 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 (oil
Ether：Ethyl acetate=10:1, Rf=0.5, ultraviolet 254nm colour developings), tracking reaction is to terminal.Add pure water in organic faciess
100mL is washed, point liquid, then is washed with 100mL saturated nacl aqueous solutions, and point liquid, organic faciess are dried with anhydrous Na 2SO4, concentration
Crude product.Crude product 10mL dichloromethane dissolves, and adds the silica gel 7g of 100-200 mesh, decompression to be spin-dried for mixing sample, uses 100g
The silica gel column chromatography post separation of 100-200 mesh, eluant petroleum ether：Ethyl acetate=80:1 slowly eluting, concentration, dry after
Arrive target product
(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
Two Herba Pelargonii Graveolentiss alcohol ester of target product pyridine -3,5- dioctyl phthalate and two-β of pyridine -3,5- dioctyl phthalate-ionol esters carry out structural table
Levy, concrete data are as follows：
Two Herba Pelargonii Graveolentiss alcohol ester (as Figure 1-3) of pyridine -3,5- dioctyl phthalate：Colourless oil liquid.1H NMR(400MHz,
CDCl3) δ ppm 9.36 (s, 2H), 8.87 (s, 1H), 5.48 (q, J=6.85,6.85,6.82Hz, 2H), 5.10 (dd, J=
14.20,7.50Hz, 2H), 4.89 (dd, J=13.30,7.25Hz, 2H), 2.22-2.07 (m, 8H), 1.62 (d, J=
12.00Hz, 6H), 1.67 (s, 6H), 1.79 (t, J=8.25,8.25Hz, 6H)；13C NMR(400MHz,CDCl3)δppm
164.54,154.15,143.38,138.01,131.95,126.31,123.63,117.70,62.64,39.55,26.26,
25.69,17.72,16.62；HRMS:m/z(ESI)[M+H]+Theoretical value 440.2801, measured value 440.2791.
Two-β of pyridine-3,5- dioctyl phthalate-ionol esters (as Figure 4-Figure 6)：Colourless oil liquid.1H NMR
(400MHz,CDCl3) δ ppm 9.36 (d, J=2.05Hz, 2H), 8.85 (t, J=1.89,1.89Hz, 1H), 6.25 (d, J=
15.87Hz, 2H), 5.69 (p, J=6.51,6.51,6.48,6.48Hz, 2H), 5.59-5.48 (m, 2H), 1.97 (t, J=
6.07,6.07Hz, 4H), 1.66 (s, 6H), 1.60 (dd, J=7.84,4.17Hz, 4H), 1.53 (s, 3H), 1.52 (s, 3H),
1.45 (dd, J=5.93,2.47Hz, 4H), 0.99 (s, 1H), 0.97 (s, 12H)；13C NMR(400MHz,CDCl3)δ
ppm163.80,154.00,137.91,136.37,132.08,131.18,129.49,126.66,73.60,39.31,33.88,
32.65,28.65,21.31,20.66,19.19.[M+Na]+found 542.3245(calcd.542.3246).
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 two-β of two Herba Pelargonii Graveolentiss alcohol ester of pyridine -3,5- dioctyl phthalate and pyridine -3,5- dioctyl phthalate -
Ionol esters.
(2) perfuming research of the target product in Nicotiana tabacum L.
With 95% ethanol as solvent, by target product pyridine -3, two Herba Pelargonii Graveolentiss alcohol ester of 5- dioctyl phthalate and pyridine -3,5- dioctyl phthalate
Two-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 pyridine -3,5- dioctyl phthalate of table, two Herba Pelargonii Graveolentiss alcohol ester
The perfuming smoking result of 2 pyridine -3,5- dioctyl phthalate of table, two-β-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. a kind of cigarette latent perfume monomer pyridine -3, the preparation method of 5- diformic esters, it is characterised in that comprise the steps：Take
Pyridine -3,5- dioctyl phthalate and single hydroxyl alcohol are dissolved in dry dichloromethane, stir 10min-30min, add 4- dimethylaminos
Pyridine (DMAP) and 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl), are stirred at room temperature 4-12h,
TLC monitoring reactions, track reaction end, and 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 cigarette latent perfume monomer pyridine -3,5- bis-
Formate ester.
2. cigarette as claimed in claim 1 latent perfume monomer pyridine -3, the preparation method of 5- diformic esters, it is characterised in that：
Described column chromatography for separation eluent is ethyl acetate and petroleum ether, both volume ratios 100:1-20:1.
3. cigarette as claimed in claim 1 latent perfume monomer pyridine -3, the preparation method of 5- diformic esters, it is characterised in that：
The molar ratio of described pyridine -3,5- dioctyl phthalate and single hydroxyl alcohol is 0.9:1-1:Between 0.9.
4. cigarette as claimed in claim 1 latent perfume monomer pyridine -3, the preparation method of 5- diformic esters, it is characterised in that：
Described single hydroxyl alcohol is geraniol or ionol, and when single hydroxyl alcohol is geraniol, the product for obtaining is pyridine -3,5- bis-
Two Herba Pelargonii Graveolentiss alcohol ester of formic acid, when single hydroxyl alcohol be ionol when, the product for obtaining be pyridine -3, two-β of 5- dioctyl phthalate-violet
Alcohol ester, both structural formulas are as follows：
5. the cigarette that prepared by a kind of method as any one of claim 1-4 is increased as Nicotiana tabacum L. with latent perfume monomer benzenpropanoic acid esters
Application of the pastil in Medicated cigarette, is applied in Medicated cigarette as fragrance-enhancing tobacco agent, 0.005- of the addition for tobacco shred weight
0.05%.
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| CN112625018A (en) * | 2020-12-10 | 2021-04-09 | 河南中烟工业有限责任公司 | 2, 3-dihydro-3-hydroxy-6-methyl-4H-pyran-4-one-5-O-linalyl carbonate and application thereof |
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