CN106631781A - Preparation method of cigarette precursor-aroma phenylpropionic ester and application thereof - Google Patents
Preparation method of cigarette precursor-aroma phenylpropionic ester and application thereof Download PDFInfo
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- CN106631781A CN106631781A CN201610880171.7A CN201610880171A CN106631781A CN 106631781 A CN106631781 A CN 106631781A CN 201610880171 A CN201610880171 A CN 201610880171A CN 106631781 A CN106631781 A CN 106631781A
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- cigarette
- benzenpropanoic acid
- preparation
- phenylpropionic
- ester
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- 235000019504 cigarettes Nutrition 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 150000002148 esters Chemical class 0.000 title abstract description 7
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 claims abstract description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 32
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- -1 geraniol ester Chemical class 0.000 claims abstract description 24
- GLZPCOQZEFWAFX-UHFFFAOYSA-N KU0063794 Natural products CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000012074 organic phase 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 10
- 239000007832 Na2SO4 Substances 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
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004440 column chromatography Methods 0.000 claims abstract description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 18
- 239000002304 perfume Substances 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 241000208125 Nicotiana Species 0.000 claims description 14
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 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
- 239000003480 eluent Substances 0.000 claims description 4
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 claims description 2
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- 238000001035 drying Methods 0.000 abstract description 7
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 abstract description 6
- CNOPDZWOYFOHGN-BQYQJAHWSA-N Beta-Ionol Chemical compound CC(O)\C=C\C1=C(C)CCCC1(C)C CNOPDZWOYFOHGN-BQYQJAHWSA-N 0.000 abstract description 5
- CNOPDZWOYFOHGN-UHFFFAOYSA-N beta-ionol Natural products CC(O)C=CC1=C(C)CCCC1(C)C CNOPDZWOYFOHGN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000000779 smoke Substances 0.000 abstract description 2
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 abstract 1
- 238000002955 isolation Methods 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- KNWQLFOXPQZGPX-UHFFFAOYSA-N methanesulfonyl fluoride Chemical compound CS(F)(=O)=O KNWQLFOXPQZGPX-UHFFFAOYSA-N 0.000 abstract 1
- 235000011152 sodium sulphate 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 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
- 206010013786 Dry skin Diseases 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
- 239000000523 sample Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010898 silica gel chromatography 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
- UZFLPKAIBPNNCA-BQYQJAHWSA-N alpha-ionone Chemical compound CC(=O)\C=C\C1C(C)=CCCC1(C)C UZFLPKAIBPNNCA-BQYQJAHWSA-N 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
- 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
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 235000013599 spices Nutrition 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
- A24B15/301—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances by aromatic compounds
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B3/00—Preparing tobacco in the factory
- A24B3/12—Steaming, curing, or flavouring tobacco
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention discloses a preparation method of cigarette precursor-aroma phenylpropionic ester. The preparation method includes steps of dissolving phenylpropionic acid and monohydric alcohol in dried methylene dichloride; stirring for 10-30 minutes, and adding 4-dimethylamino pyridine and 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride; stirring for 4-12h under room temperature; monitoring reaction by TLC and tracking the reaction end point; adding water in an organic phase and washing; separating liquid, and washing the mixture by saturated sodium chloride solution; separating liquid and drying the organic phase by anhydrous Na2SO4; concentrating and acquiring the crude product; performing column chromatography isolation to obtain the cigarette precursor-aroma phenylpropionic ester. In the invention, phenylpropionic geraniol ester, phenylpropionic-beta-ionol ester can significantly improve the addition in cigarette by comparing with geraniol and beta-ionol matrix; the external aroma variety of the cigarette is not influenced; the cigarette precursor-aroma phenylpropionic ester is applied to cigarette as the cigarette fumette, thus the cigarette thrill and offensive odor can be reduced, and the smoke roundness and comfort can be improved.
Description
Technical field
The present invention relates to essence and flavoring agent and tobacco manufacture field, specifically a kind of cigarette system of latent perfume monomer benzenpropanoic acid esters
Preparation Method and its application.
Background technology
Many excellent spices are because its high high-temp stability is poor, volatility compared with it is strong, fragrance remaining time is short the problems such as limit
It 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 itself is without perfume
Gas, but can discharge with fragrance fragrance through chemical hydrolysis, enzymolysis or the approach such as microbial action, pyrolysis, photodestruciton
Compound.Because of its security preferably, listed in natural perfume material category in the world, with it some local flavor flavoring essence effects are allocated
Very well.Different from volatility and half volatile fragrance matter, perfume class compound of diving is reducing artificial flavor and taste compensation vestige
The significant changes of the material delivering amount such as nicotine in cigarette mainstream flue gas, tar are not result in simultaneously, more longlasting can stably provide 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 benzenpropanoic acid esters is planted, and inquires into its application in perfuming cigarette.
The 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 benzenpropanoic acid esters
Preparation method and its application in 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 Phenpropionate, it comprises the steps：
Take benzenpropanoic acid and single hydroxyl alcohol is 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 water washing, point liquid are added in organic phase, then are washed with saturated nacl aqueous solution, point liquid,
Organic phase anhydrous Na2SO4It is dried, is concentrated to give crude product, then carries out column chromatography for separation and obtain final product the cigarette monomer perfume phenylpropyl alcohol
Acid esters.
Further, described column chromatography for separation eluent is that ethyl acetate and petroleum ether mix, both volume ratios
100:1-20:1。
Further, the molar ratio of described benzenpropanoic 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, is obtained
Product is benzenpropanoic acid spiceleaf alcohol ester, and when single hydroxyl alcohol is ionol, the product for obtaining is benzenpropanoic acid-β-ionol esters,
Both structural formulas are as follows：
Further, the cigarette that prepared by method as defined above is with latent perfume monomer benzenpropanoic acid esters as fragrance-enhancing tobacco agent in cigarette
In application, be applied in cigarette as fragrance-enhancing tobacco agent, addition for pipe tobacco weight 0.01-0.05%
The compounds of this invention benzenpropanoic acid spiceleaf alcohol ester and benzenpropanoic acid-β-ionol esters are a kind of latent aroma compounds, normal temperature
Down its is stable in properties, is colourless liquid, but it passes through heating cleavable generation tool and is significantly increased tobacco aroma material, such as 3- oxygen
Generation-alpha, beta-lonone, geraniol, monoterpene vinyl compound.
Compared to the prior art, beneficial effects of the present invention：
1. the present invention prepares benzenpropanoic acid spiceleaf alcohol ester and benzenpropanoic acid-β-ionol esters compared with geraniol and β-ionol mother
Body thing, can significantly improve the addition in cigarette, and not affect the outer fragrant kind of cigarette.
2. the present invention is with DMAP/1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate
Benzenpropanoic acid and geraniol, β-ionol esterification reaction condensation reagent, can significantly improve reaction yield, simplify post processing work
Skill.
3. two kinds of cigarette monomer perfumes that the present invention is developed, are applied in cigarette first as fragrance-enhancing tobacco agent,
The excitant and miscellaneous gas of cigarette can be reduced, the mellow and full sense of cigarette smoke and comfortableness is improved.
Description of the drawings
Fig. 1 is benzenpropanoic acid spiceleaf alcohol ester 1H NMR nuclear magnetic spectrograms；
Fig. 2 is benzenpropanoic acid spiceleaf alcohol ester 13C NMR nuclear magnetic spectrograms；
Fig. 3 is benzenpropanoic acid spiceleaf alcohol ester HRMS high-resolution spectrograms；
Fig. 4 is benzenpropanoic acid-β-ionol 1H NMR nuclear magnetic spectrograms；
Fig. 5 is benzenpropanoic acid-β-ionol 13C NMR nuclear magnetic spectrograms；
Fig. 6 is benzenpropanoic 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 aromaticss monomer benzenpropanoic acid spiceleaf alcohol ester：
Take 10mmol geraniols and 10mmol benzenpropanoic acids are dissolved in the dichloromethane of 100ml dryings, after stirring 10min, plus
Enter DMAP (DMAP) (5mmol) and 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate
(EDCHCl) (11mmol), it is stirred at room temperature, TLC monitoring reaction (petroleum ethers：Ethyl acetate=10:1, Rf=0.5, ultraviolet 254nm
Colour developing), track reaction end.The 50mL that adds water in organic phase is washed, point liquid, then is washed with 50mL saturated nacl aqueous solutions, point
Liquid, organic phase anhydrous Na2SO4It is dried, is 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 wash-out, after concentration, drying target product is obtained.
Embodiment two
The preparation method of tobacco aromaticss monomer benzenpropanoic acid spiceleaf alcohol ester：
Take 10mmol geraniols and 1.05mmol benzenpropanoic acids are dissolved in the dichloromethane of 100ml dryings, after stirring 10min,
Add DMAP (DMAP) (4mmol) and 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate
(EDCHCl) (11mmol), it is stirred at room temperature, TLC monitoring reaction (petroleum ethers：Ethyl acetate=10:1, Rf=0.5, ultraviolet 254nm
Colour developing), track reaction end.The 50mL that adds water in organic phase is washed, point liquid, then is washed with 50mL saturated nacl aqueous solutions, point
Liquid, organic phase anhydrous Na2SO4It is dried, is 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 wash-out, after concentration, drying target product is obtained.
Embodiment three
The preparation method of tobacco aromaticss monomer benzenpropanoic acid-β-ionol esters：
In there-necked flask, the 20mmol β-ionol for weighing and 10mmol benzenpropanoic acids is added to be dissolved in 200ml dryings
In dichloromethane, after stirring 10min, add DMAP (DMAP) (10mmol) and 1- ethyls-(3- dimethylaminos
Propyl group) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl) (22mmol), under room temperature stir, TLC monitoring reaction (petroleum ether：Acetic acid second
Ester=10:1, Rf=0.5, ultraviolet 254nm colour developings), tracking reaction is to terminal.Add pure water 100mL washings in organic phase, point
Liquid, then washed with 100mL saturated nacl aqueous solutions, point liquid, organic phase anhydrous Na2SO4It is dried, the crude product of concentration.Crude product
Dissolved with 10mL dichloromethane, add the silica gel 7g of 100-200 mesh, decompression is spin-dried for mixing sample, with the silica gel of 100g 100-200 mesh
Chromatography post separation, eluant, eluent petroleum ether：Ethyl acetate=80:1 slowly elutes, concentrate, be dried after obtain target product
Example IV
The preparation method of tobacco aromaticss monomer benzenpropanoic acid-β-ionol esters：
In there-necked flask, the 20mmol β-ionol for weighing and 21mmol benzenpropanoic acids is added to be dissolved in 200ml dryings
In dichloromethane, after stirring 10min, add DMAP (DMAP) (8mmol) and 1- ethyls-(3- dimethylaminos
Propyl group) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl) (22mmol), under room temperature stir, TLC monitoring reaction (petroleum ether：Acetic acid second
Ester=10:1, Rf=0.5, ultraviolet 254nm colour developings), tracking reaction is to terminal.Add pure water 100mL washings in organic phase, point
Liquid, then washed with 100mL saturated nacl aqueous solutions, point liquid, organic phase anhydrous Na2SO4It is dried, the crude product of concentration.Crude product
Dissolved with 10mL dichloromethane, add the silica gel 7g of 100-200 mesh, decompression is spin-dried for mixing sample, with the silica gel of 100g 100-200 mesh
Chromatography post separation, eluant, eluent petroleum ether：Ethyl acetate=80:1 slowly elutes, concentrate, be dried after obtain target product.
(1) structural characterization of target product
As red high resolution mass spectrum (HR-MS), carbon-13 nmr spectra (1H-NMR 13C-NMR) respectively to obtained by embodiment
Target product benzenpropanoic acid spiceleaf alcohol ester and benzenpropanoic acid-β-ionol esters carry out structural characterization, and concrete data are as follows：
As Figure 1-3, benzenpropanoic acid geraniol ester：Colourless oil liquid.1H NMR(400MHz,CDCl3)δppm 7.18-
7.29 (m, 5H), 5.31 (t, J=6.10,6.10Hz, 1H), 5.08 (s, 1H), 4.63-4.53 (m, 2H), 2.95 (t, J=
7.76,7.76Hz, 2H), 2.62 (dd, J=10.02,5.54Hz, 2H), 2.06 (dd, J=14.68,6.04Hz, 4H), 1.75
(d, J=9.62Hz, 3H), 1.68 (s, 3H), 1.65-1.56 (m, 3H)；13C NMR(400MHz,CDCl3)δppm172.92,
142.28,140.62,131.84,128.51,128.34,126.26,123.80,119.22,118.33,61.43,39.57,
36.01,31.06,26.34,25.74,17.74,16.51；HRMS:m/z(ESI)[M+Na]+Theoretical value 309.1830, measured value
309.1830。
As Figure 4-Figure 6, benzenpropanoic acid-β-ionol esters：Colourless oil liquid.1H NMR(400MHz,CDCl3)δ
Ppm7.29-7.25 (m, 2H), 7.19 (dd, J=11.29,4.55Hz, 2H), 6.09 (d, J=13.95Hz, 1H), 5.43-
5.33 (m, 2H), 3.01-2.89 (m, 2H), 2.66-2.56 (m, 2H), 1.96 (t, J=6.00,6.00Hz, 2H), 1.63 (s,
3H), 1.61-1.57 (m, 2H), 1.46-1.41 (m, 2H), 1.35-1.29 (m, 3H), 0.97 (t, J=7.49,7.49Hz,
6H)；13C NMR(400MHz,CDCl3)δppm172.17,140.64,136.55,132.83,130.07,129.05,128.45,
128.30,126.19,71.74,39.35,36.28,33.89,32.65,31.05,28.65,21.30,20.60,19.23.[M+
Na]+found 349.2142(calcd.349.2143).
From spectrum elucidation analysis, with reference to infrared spectrum (IR), high resolution mass spec (1HR-MS) and carbon-13 nmr spectra
(13C-NMR) can determine that gained compound is benzenpropanoic acid spiceleaf alcohol ester and benzenpropanoic acid-β-ionol esters.
(2) perfuming research of the target product in tobacco
With 95% ethanol as solvent, target product benzenpropanoic acid spiceleaf alcohol ester and benzenpropanoic acid-β-ionol esters are matched somebody with somebody respectively
Into the solution of mass fraction 1%.The above-mentioned solution containing target product of 0.5g, 1.0g, 5.0g, 10.0g and 15.0g is taken respectively, so
Uniform spray afterwards is added in the 100g blank cigarette shreds of five parts of non-flavoring and casings, is rolled, and respectively picks out 100 same weight volumes
Cigarette, is placed in 22 DEG C ± 1 DEG C of temperature, and in the climatic chamber of humidity 60% ± 2% 48h is balanced, and smokes panel test.Control sample is blank coil
Cigarette, control sample equally balances 48h under the conditions of identical epidemic disaster.
The perfuming smoking result of the benzenpropanoic acid-β of table 1-ionol esters
The perfuming smoking result of the benzenpropanoic acid spiceleaf alcohol ester of table 2
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 be readily occurred in, all should
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 preparation method of latent perfume monomer benzenpropanoic acid esters, it is characterised in that：Comprise the steps：
Take benzenpropanoic acid and single hydroxyl alcohol is 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 is anti-
Terminal is answered, water washing, point liquid are added in organic phase, then washed with saturated nacl aqueous solution, point liquid, organic phase anhydrous Na2SO4
It is dried, is concentrated to give crude product, then carries out column chromatography for separation and obtain final product the cigarette monomer perfume Phenpropionate.
2. the cigarette as claimed in claim 1 preparation method of latent perfume monomer benzenpropanoic acid esters, it is characterised in that：Described post layer
Analyse the mixing that separation eluent is ethyl acetate and petroleum ether, both volume ratios 100:1-20:1.
3. the cigarette as claimed in claim 1 preparation method of latent perfume monomer benzenpropanoic acid esters, it is characterised in that：Described phenylpropyl alcohol
The molar ratio of acid and single hydroxyl alcohol is 0.9:1-1:Between 0.9.
4. the cigarette as claimed in claim 1 preparation method of latent perfume monomer benzenpropanoic acid esters, it is characterised in that：Described single hydroxyl
Base alcohol is geraniol or ionol, and when single hydroxyl alcohol is geraniol, the product for obtaining is benzenpropanoic acid spiceleaf alcohol ester, when single hydroxyl
When base alcohol is ionol, the product for obtaining is benzenpropanoic acid-β-ionol esters, and 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 with latent perfume monomer benzenpropanoic acid esters as tobacco
Application of the pastil in cigarette, is applied in cigarette as fragrance-enhancing tobacco agent, and addition is the 0.01- of pipe tobacco weight
0.05%.
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| CN201610880171.7A CN106631781A (en) | 2016-10-09 | 2016-10-09 | Preparation method of cigarette precursor-aroma phenylpropionic ester and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111685362A (en) * | 2019-03-12 | 2020-09-22 | 湖南中烟工业有限责任公司 | Tobacco sheet containing 5-hydroxy acid alcohol ester and preparation method and application thereof |
| CN113277947A (en) * | 2021-06-04 | 2021-08-20 | 安徽中烟工业有限责任公司 | Monomer spice 3- (2-hydroxyphenyl) propionic acid-2 hydroxypropyl ester for cigarette and synthetic method and application thereof |
| CN113461535A (en) * | 2021-08-05 | 2021-10-01 | 四川三联新材料有限公司 | Geraniol ambroxol carbonate latent aromatic, and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111685362A (en) * | 2019-03-12 | 2020-09-22 | 湖南中烟工业有限责任公司 | Tobacco sheet containing 5-hydroxy acid alcohol ester and preparation method and application thereof |
| CN113277947A (en) * | 2021-06-04 | 2021-08-20 | 安徽中烟工业有限责任公司 | Monomer spice 3- (2-hydroxyphenyl) propionic acid-2 hydroxypropyl ester for cigarette and synthetic method and application thereof |
| CN113277947B (en) * | 2021-06-04 | 2023-10-03 | 安徽中烟工业有限责任公司 | 3- (2-hydroxyphenyl) propionic acid-2-hydroxypropyl ester as cigarette monomer spice and synthesis method and application thereof |
| CN113461535A (en) * | 2021-08-05 | 2021-10-01 | 四川三联新材料有限公司 | Geraniol ambroxol carbonate latent aromatic, and preparation method and application thereof |
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