CN106858710A - It is a kind of to improve benzisoxa furfuran compound of cigarette smoking effect and preparation method and application - Google Patents
It is a kind of to improve benzisoxa furfuran compound of cigarette smoking effect and preparation method and application Download PDFInfo
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- CN106858710A CN106858710A CN201710214697.6A CN201710214697A CN106858710A CN 106858710 A CN106858710 A CN 106858710A CN 201710214697 A CN201710214697 A CN 201710214697A CN 106858710 A CN106858710 A CN 106858710A
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- 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
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/06—Use of materials for tobacco smoke filters
- A24D3/14—Use of materials for tobacco smoke filters of organic materials as additive
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
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Abstract
Can improve benzisoxa furfuran compound of cigarette smoking effect and preparation method and application the present invention relates to a kind of, belong to technical field of phytochemistry.The compound is isolated from tobacco, and Compound nomenclature is：The dimethyl 2 of 6,8 dihydro, 5 methoxyl group 2,2HFurans [3,4g] chromene, it is English entitled：6,8 dihydro, 5 methoxy 2,2 dimethyl 2H furo [3,4 g] chromene, its molecular formula is C14H16O3, structure such as formula（I）It is shown：, formula（I）；Its preparation method is, with tobacco as raw material, to be obtained through medicinal extract extraction, organic solvent extraction, MCI decolourings, silica gel column chromatography and high performance liquid chromatography separation step.The compounds of this invention is added in cigarette filter, can increase the fragrance of cigarette, improves the sweet sense of cigarette smoke, prominent sense of promoting the production of body fluid, and lifts the suction quality of cigarette.
Description
Technical field
The invention belongs to technical field of phytochemistry, and in particular to a kind of to extract the benzisoxa furan for obtaining first from tobacco
Class of muttering compound and preparation method thereof.Meanwhile, the compounds of this invention is added in cigarette filter, with preferable flavouring effect
Really；And compared with control, the sweet sense of cigarette smoking has lifting, the effect of promoting the production of body fluid obvious, and suction comfortableness is substantially changed
It is kind.
Background technology
Tobacco drafts a document that Solanaceae tobacco is annual or limited herbaceos perennial, wherein being cultivated with tobacco N.tabacum L.
Most wide, its ripe blade is the important source material of cigarette industry, is a kind of economic worth crop higher.Tobacco removes and is mainly used in
Suck outer, also other relatively broad purposes.Meanwhile, tobacco is the plant of chemical composition complexity the most in the world, secondary generation
Thank to product to enrich very much, by the research of decades, people identify the monomer chemistries material for coming from tobacco and just exceed at present
Kind more than 3000, and also many compositions not yet identify come.
Research shows, outside the routine chemical componentses such as isolating protein, amino acid, sugar, phosphorus, calcium, potassium, also containing a large amount of in tobacco
Secondary metabolite, type of compounds includes flavones, cumarin, tannin, furans, benzisoxa furans, Phenylpropanoid Glycosides, terpene, biology
Alkali etc..These compounds have multiple biological activities, in antibacterial, anti-inflammatory, anti-mutation, step-down, clearing heat and detoxicating, calm, diuresis, anti-
The many aspects such as oxidation, anticancer, anti-cancer, suppression lipase have remarkable result.Furfuran compound belongs to heterocyclic, natural
Also there is the document report for being widely present such compound in plant.In addition to extensive pharmacological action, furans or a class weight
The volatile compound wanted, is naturally occurring in various fruit and spice berry, such compound be widely used in various beverages,
In the formula of the flavoring essences such as bakery product.
A kind of present invention isolated benzisoxa furfuran compound from tobacco, the compound is added to tobacco smoke filter element
In mouth, there is preferable flavouring effect to cigarette；And compared with control, the moisture feeling of cigarette smoking has lifting, the effect of promoting the production of body fluid
Substantially, suction comfortableness be improved significantly, relevant report is not yet found at present.
The content of the invention
The first object of the present invention is to provide a kind of benzisoxa furfuran compound；Second purpose is to provide the benzene
And the preparation method of different furfuran compound；3rd purpose is to provide the benzisoxa furfuran compound to add in cigarette filter
Application in perfume (or spice), is mainly used in improving cigarette smoking quality.
To achieve the above object, the technical solution adopted by the present invention is as follows：
The first object of the present invention is achieved in that a kind of benzisoxa furans chemical combination that can improve cigarette smoking effect
Thing is isolated from tobacco, and its molecular formula is C14H16O3, shown in structure such as formula (I)：
The compound is light yellow gum thing, and Compound nomenclature is：6,8- dihydro -5- methoxyl group -2,2- dimethyl -2H-
Furans [3,4-g] chromene, English is entitled：6,8-dihydro-5-methoxy-2,2-dimethyl-2H-furo[3,4-g]
chromene。
The second object of the present invention is achieved in that the above-mentioned benzisoxa furans chemical combination that can improve cigarette smoking effect
The preparation method of thing, with tobacco as raw material, through medicinal extract extraction, organic solvent extraction, MCI decolourings, silica gel column chromatography and efficient liquid
Phase chromatrographic separation step is obtained, specially：
A, medicinal extract are extracted：Tobacco is crushed to 20~40 mesh, 2~5 are extracted with 5~10 times of solvent supersonics of tobacco weight
It is secondary, 30~60 minutes every time, merge extract solution and filter, filtrate decompression is concentrated into the 1/4 of original volume, stands, and filters sediment,
Gained filtrate decompression is condensed into medicinal extract a afterwards；
B, organic solvent extraction：To the water that weight is 1~2 times of medicinal extract a weight is added in medicinal extract a, then with the body such as water
Long-pending organic solvent is extracted 3~5 times, merges organic solvent extraction phase, and the organic solvent extraction phase decompression for obtaining will be merged afterwards
It is condensed into medicinal extract b；
C, MCI decolourize：It is that 50~100% methyl alcohol are water-soluble to the volumetric concentration that addition in medicinal extract b is 3~5 times of medicinal extract b weight
Liquid, after medicinal extract b is completely dissolved, upper MCI posts are that 90%-95% methanol aqueous solutions are eluted with volumetric concentration, merge wash-out
Liquid, is concentrated under reduced pressure into medicinal extract c by the eluent after merging afterwards；
D, silica gel column chromatography：By silica gel column chromatography on medicinal extract c, dress post silica gel is 160~200 mesh, and consumption is medicinal extract c weight
6~10 times of amounts；It is 1 with volume ratio:0~0:1 chloroform and acetone mixed organic solvents gradient elution, collects the gradient of each gradient
Eluent is simultaneously concentrated under reduced pressure, and is monitored through TLC, merges identical part；
E, high performance liquid chromatography separation：It is 7 by volume ratio:The eluent that 3 chloroform-acetone is afforded, through efficient liquid
Phase chromatographic separation and purification, obtains final product described benzisoxa furfuran compound.
It is further preferred that the solvent of the step A is aqueous acetone solution, volume that volumetric concentration is 70~100%
The methanol aqueous solution that concentration is 90~100% ethanol water or volumetric concentration is 90~100%.
It is further preferred that the organic solvent of the step B is dichloromethane, chloroform, ethyl acetate, ether or stone
Oily ether.
It is further preferred that medicinal extract c is first medicinal extract c 1.5 with weight before through silica gel column chromatography in the D steps
~3 times of acetone or methyl alcohol dissolving, is then 80~100 mesh silica gel mixed samples of 0.8~1.2 times of medicinal extract c with weight, afterwards
Loading.
It is further preferred that in the D steps, during gradient elution, the chloroform and acetone mixed organic solvents for being used
Volume ratio be followed successively by 20:1、9:1、8:2、7:3、6:4 and 1:1, each gradient elution to TLC point plates without point after (the i.e. gradient
After can not eluting material), change next gradient elution.
It is further preferred that the E steps high performance liquid chromatography separation purifying be with 40% methyl alcohol for flow
Phase, 15~25ml/min of flow velocity, with 21.2 × 250mm, 5 μm of Zorbax PrepHT GF reverse phase preparative columns are fixing phase, purple
External detector Detection wavelength is 280nm, the μ L of each sample introduction 10~100, collects the chromatographic peak of 35.2min, is evaporated after repeatedly adding up.
The structure of the benzisoxa furfuran compound that method described above is prepared is measured by the following method：
The compounds of this invention is light yellow gum thing；
HRESI-MS shows that its quasi-molecular ion peak is 255.0990 [M+Na]+(calculated value 255.0997), with reference to1H NMR
Determine that its molecular formula is C with DEPT spectrums14H16O3, degree of unsaturation is 7.
Aromatic ring (1612,1568 and 1464cm are shown in infrared spectrum-1) resonance absorbing peak.And ultraviolet spectra 210,
245th, 280nm has absorption maximum to there may be aromatic ring structure in also illustrate that compound.
Compound1H and13C H NMR spectroscopies (such as table 1, Fig. 1 and Fig. 2) show that it contains 14 carbon and 16 hydrogen, including 1
1,2,4,5- quaternary phenyl ring (C-4~C-7, C-4a and C-7a, H-7), 1 humorous dimethyl chromene ring (C-1'~C-5', H-
1', H-2' and H6- 4', 5'), two methylene (C-1 and C-3 of oxidation；H2- 1 and H2-3)；And 1 methoxyl group (δC
61.2；δH3.85).Its HMBC coherent signal is further analyzed, according to H2- 1 and C-3, C-4a, C-7, C-7a；H2- 3 and C-1,
C-4、C-4a、C-7a；And H-7 (such as Fig. 3) related to the HMBC of C-1, C-4a, C-7a can speculate that compound is benzisoxa furans
Class formation.
H-1' and C-4, C-5, C-6 can be observed in the HMBC spectrums of compound；H-2' and C-5, and H-4's and C-1' is remote
Cheng Xiangguan, can speculate that humorous dimethyl chromene ring is substituted in C-5 and C-6 of compound, and C-1' carbon is connected to phenyl ring
C-5；Methoxy substitution can be by methoxyl group hydrogen (δ at C-4H3.85) with C-4 (δC156.3) HMBC correlations are determined.
So far, the structure of compound determined, and is named as Compound nomenclature and is：6,8- dihydro -5- methoxyl groups -2,2-
Dimethyl -2H- furans [3,4-g] chromene.
Infrared, the ultraviolet and mass spectrometric data of compound：UV (methyl alcohol), λmax(logε)280(3.90)、245(3.64)、210
(4.12)nm；IR (pressing potassium bromide troche)：νmax 3070、2963、1612、1568、1464、1334、1269、1159、1046、
894cm-1；1H and13C NMR datas (500 and 125MHz, CDCl3), it is shown in Table 1；[the M+Na of positive ion mode ESIMS m/z 255
]+；Positive ion mode HRESIMS m/z 255.0990 [M+Na]+(calculated value C14H16NaO3, 255.0997).
The compounds of this invention of table 1.1H NMR and13C NMR datas (CDCl3)
| No. | No. | ||||
| 1 | 75.0 | 5.11 | 7a | 14 | |
| 3 | 73.0 | 5.14 | 1′ | 11 | 6.65 |
| 4 | 156. | 2′ | 12 | 5.87 | |
| 5 | 110. | 3′ | 7 | ||
| 6 | 154. | 4′ | 2 | 1.57s | |
| 7 | 103. | 6.29 | 5′ | 2 | 1.57s |
| 4a | 124. | -OM | 6 | 3.85s |
What the third object of the present invention was realized in：
The present invention can improve the benzisoxa furfuran compound of cigarette smoking effect as preparing cigarette filter-tip additive agent
Using.
The present invention is that cigarette filter is molded the most frequently used plasticizer, and the compounds of this invention in view of triacetyl glycerine
Triacetyl glycerine is dissolved in, in cigarette filter forming process, the compounds of this invention is added to filtering by triacetyl glycerine
In mouth, easily realized in technique, and do not increase the additional step in production process.
For cigarette " purple cloud, " that addition cigarette is Hong Yun Red River group with triacetyl glycerine by above-mentioned benzisoxa furans
The compound solution for being made into 0.1mg/mL, 0.2mg/mL and 0.3mg/mL.Uniformly sprayed by the 5%-8% of filter tow weight
It is spread across on filter tow, is made filter stick, the filter stick is then made cigarette by conventional cigarette cigarette, carries out sensory evaluation,
And to be not added with the identical cigarette of the compound as control.Evaluation and analysis result shows：Compared with control, cigarette smoking it is sweet
Sense be obviously improved, promote the production of body fluid sense protrude, suction comfortableness be improved significantly.
Compared with prior art, its advantage is the present invention：
Benzisoxa furfuran compound of the present invention is separated from tobacco first, by nuclear magnetic resonance and mass spectrum
It is benzisoxa furfuran compound that assay method is determined, and characterizes its concrete structure.Experiment proves that the compounds of this invention adds
It is added in cigarette filter, the fragrance of cigarette can be increased, improve the sweet sense of cigarette smoke, prominent sense of promoting the production of body fluid, lifts taking out for cigarette
Inhale quality.
Brief description of the drawings
Fig. 1 be benzisoxa furfuran compound of the present invention carbon-13 nmr spectra (13C NMR)；
Fig. 2 be benzisoxa furfuran compound of the present invention proton nmr spectra (1H NMR)；
Fig. 3 is the related figures of crucial HMBC of benzisoxa furfuran compound of the present invention.
Specific embodiment
With reference to embodiment, the present invention is described in further detail.
It will be understood to those of skill in the art that the following example is merely to illustrate the present invention, and should not be regarded as limiting this hair
Bright scope.In the examples where no specific technique or condition is specified, according to the technology or condition described by document in the art
Or carried out according to product description.Agents useful for same or the unreceipted production firm person of instrument, being can be by buying what is obtained
Conventional products.
Benzisoxa furfuran compound of the present invention, is isolated from tobacco, and its molecular formula is C14H16O3, knot
Shown in structure such as formula (I)：
Compound nomenclature is：6,8- dihydro -5- methoxyl group -2,2- dimethyl -2H- furans [3,4-g] chromene, English name
For：6,8-dihydro-5-methoxy-2,2-dimethyl-2H-furo[3,4-g]chromene.
The preparation method of benzisoxa furfuran compound of the present invention, be with tobacco as raw material, through medicinal extract extract, it is organic
Solvent extraction, MCI are decolourized, silica gel column chromatography and high performance liquid chromatography separation step are obtained, specially：
A, medicinal extract are extracted：Tobacco is crushed to 20~40 mesh, 2~5 are extracted with 5~10 times of solvent supersonics of tobacco weight
It is secondary, 30~60 minutes every time, merge extract solution and filter, filtrate decompression is concentrated into the 1/4 of original volume, stands, and filters sediment,
Gained filtrate decompression is condensed into medicinal extract a afterwards；
B, organic solvent extraction：To the water that weight is 1~2 times of medicinal extract a weight is added in medicinal extract a, then with the body such as water
Long-pending organic solvent is extracted 3~5 times, merges organic solvent extraction phase, and the organic solvent extraction phase decompression for obtaining will be merged afterwards
It is condensed into medicinal extract b；
C, MCI decolourize：It is that 50~100% methyl alcohol are water-soluble to the volumetric concentration that addition in medicinal extract b is 3~5 times of medicinal extract b weight
Liquid, after medicinal extract b is completely dissolved, upper MCI posts are that 90%-95% methanol aqueous solutions are eluted with volumetric concentration, merge wash-out
Liquid, is concentrated under reduced pressure into medicinal extract c by the eluent after merging afterwards；
D, silica gel column chromatography：By silica gel column chromatography on medicinal extract c, dress post silica gel is 160~200 mesh, and consumption is medicinal extract c weight
6~10 times of amounts；It is 1 with volume ratio:0~0:1 chloroform and acetone mixed organic solvents gradient elution, collects the gradient of each gradient
Eluent is simultaneously concentrated under reduced pressure, and is monitored through TLC, merges identical part；
E, high performance liquid chromatography separation：It is 7 by volume ratio:The eluent that 3 chloroform-acetone is afforded, through efficient liquid
Phase chromatographic separation and purification, obtains final product described benzisoxa furfuran compound.
The solvent of the step A is aqueous acetone solution that volumetric concentration is 70~100%, volumetric concentration is 90~100%
Ethanol water or methanol aqueous solution that volumetric concentration is 90~100%.
The organic solvent of the step B is dichloromethane, chloroform, ethyl acetate, ether or petroleum ether.
Medicinal extract c is the acetone or first of 1.5~3 times of medicinal extract c with weight before through silica gel column chromatography, first in the D steps
Alcohol dissolves, and is then 80~100 mesh silica gel mixed samples of 0.8~1.2 times of medicinal extract c with weight, afterwards loading.
In the D steps, during gradient elution, the chloroform and the volume ratio of acetone mixed organic solvents for being used are followed successively by
20:1、9:1、8:2、7:3、6:4 and 1:1, after each gradient elution to TLC point plates is without point, change next gradient elution.
It with 40% methyl alcohol is mobile phase, 15~25ml/ of flow velocity that the high performance liquid chromatography separation purifying of the E steps is
Min, with 21.2 × 250mm, 5 μm of Zorbax PrepHT GF reverse phase preparative columns are fixing phase, UV-detector Detection wavelength
It is 280nm, the μ L of each sample introduction 10~100 collect the chromatographic peak of 35.2min, are evaporated after repeatedly adding up.
The compounds of this invention is added in cigarette filter, with preferable flavouring effect；And compared with control, roll up
The moisture feeling of cigarette suction has lifting, the effect of promoting the production of body fluid obvious, suction comfortableness be improved significantly.
Embodiment 1
Tobacco sample derives from Yunnan Yuxi, and kind is Yuxi K326.
Dry tobacco 4.4kg is taken, meal is broken to 30 mesh, carried with 10 times the 70% of tobacco weight of aqueous acetone solution ultrasound
Take 4 times, 60 minutes every time, extract solution merged；Extract solution is filtered, and is concentrated under reduced pressure into the 1/4 of original volume；Stand, filter sediment,
It is concentrated under reduced pressure into the medicinal extract a of 120g；
240g water is added in medicinal extract a, is extracted 5 times with the chloroform isometric with water, merge organic solvent extraction phase, decompression
It is condensed into 80g medicinal extract b；
The methyl alcohol dissolving of 240g is added in medicinal extract b, after medicinal extract b is completely dissolved, upper MCI posts are with 6 liters of volumetric concentrations
90% methanol aqueous solution is eluted, and merges eluent, is concentrated under reduced pressure to give 62g medicinal extract c；
The acetone solution of 93g is added in medicinal extract c, 100 mesh silica gel 62g is subsequently adding and is mixed sample, after mixing sample, with 200 mesh silicon
Glue 372g fills post；The chloroform and the volume ratio of acetone mixed organic solvents for being used are followed successively by 20:1、9:1、8:2、7:3、6:4 Hes
1:1, after each gradient elution to TLC point plates is without point, next gradient elution is changed, collect gradient eluent, concentrated under reduced pressure, warp
TLC is monitored, and merges identical part, obtains 6 part A-F, wherein, to the sample D (7 being collected into:3) part 12g, then with
40% methyl alcohol is mobile phase, and flow velocity 15ml/min, 21.2 × 250mm, 5 μm of Zorbax PrepHT GF reverse phase preparative columns are
Fixing phase, UV-detector Detection wavelength is 280nm, the μ L of each sample introduction 50, the chromatographic peak of 35.2min is collected, after repeatedly adding up
It is evaporated, obtains final product the benzisoxa furfuran compound.
Embodiment 2
Tobacco sample derives from Dali, and kind is cloud and mist 200.
Dry tobacco 10kg is taken, meal is broken to 40 mesh, with 5 times of methyl alcohol ultrasonic extractions of tobacco weight 5 times, every time 30
Minute, extract solution merges；Extract solution is filtered, and is concentrated under reduced pressure into the 1/4 of original volume；Stand, filter sediment, be concentrated under reduced pressure into
300g medicinal extract a；
350g water is added in medicinal extract a, is extracted 3 times with the dichloromethane isometric with water, merge organic solvent extraction phase,
It is concentrated under reduced pressure into 210g medicinal extract b；
The volumetric concentration of 630g is added in medicinal extract b for 50% methanol aqueous solution dissolves, after medicinal extract b is completely dissolved, on
MCI posts, with 10 liters of volumetric concentrations for 95% methanol aqueous solution is eluted, merge eluent, are concentrated under reduced pressure to give 150g medicinal extract c；
The acetone solution of 300g is added in medicinal extract c, 80 mesh silica gel 180g is subsequently adding and is mixed sample, with 180 mesh silica gel 1500kg
Dress post, mixes upper prop after sample；The chloroform and the volume ratio of acetone mixed organic solvents for being used are followed successively by 20:1、9:1、8:2、7:3、
6:4 and 1:1, after each gradient elution to TLC point plates is without point, next gradient elution is changed, collect gradient eluent, depressurize dense
Contracting, monitors through TLC, merges identical part, obtains 6 part A-F, wherein, to the sample D (7 being collected into:3) part 32g,
It is again mobile phase, flow velocity 25ml/min, 21.2 × 250mm, 5 μm of the anti-phase preparations of ZorbaxPrepHT GF with 40% methyl alcohol
Post is fixing phase, and UV-detector Detection wavelength is 280nm, the μ L of each sample introduction 80, collects the chromatographic peak of 35.2min, repeatedly tired
Plus after be evaporated, obtain final product the benzisoxa furfuran compound.
Embodiment 3
Tobacco sample derives from Dali, and kind is cloud and mist 200.
Dry tobacco 15kg is taken, meal is broken to 20 mesh, with 8 times the 90% of tobacco weight of methanol aqueous solution ultrasonic extraction
2 times, 45 minutes every time, extract solution merged；Extract solution is filtered, and is concentrated under reduced pressure into the 1/4 of original volume；Stand, filter sediment, subtract
Pressure is condensed into 460g medicinal extract a；
460g water is added in medicinal extract a, is extracted 4 times with the ethyl acetate isometric with water, merge organic solvent extraction phase,
It is concentrated under reduced pressure into 300g medicinal extract b；
The volumetric concentration of 1500g is added in medicinal extract b for 85% methanol aqueous solution dissolves, after medicinal extract b is completely dissolved, on
MCI posts, with 15 liters of volumetric concentrations for 93% methanol aqueous solution is eluted, merge eluent, are concentrated under reduced pressure to give 150g medicinal extract c；
The methyl alcohol dissolving of 450g is added in medicinal extract c, 100 mesh silica gel 120g is subsequently adding and is mixed sample, with 160 mesh silica gel 1.2kg
Dress post, mixes upper prop after sample；The chloroform and the volume ratio of acetone mixed organic solvents for being used are followed successively by 20:1、9:1、8:2、7:3、
6:4 and 1:1, after each gradient elution to TLC point plates is without point, next gradient elution is changed, collect gradient eluent, depressurize dense
Contracting, monitors through TLC, merges identical part, obtains 6 part A-F, wherein, to the sample D (7 being collected into:3) part 32g,
It is again mobile phase, flow velocity 20ml/min, 21.2 × 250mm, 5 μm of the anti-phase preparations of ZorbaxPrepHT GF with 40% methyl alcohol
Post is fixing phase, and UV-detector Detection wavelength is 280nm, the μ L of each sample introduction 80, collects the chromatographic peak of 35.2min, repeatedly tired
Plus after be evaporated, obtain final product the benzisoxa furfuran compound.
Embodiment 4
Embodiment 4 is with the difference of embodiment 3, and during ultrasonic extraction, solvent for use is 95% ethanol water.Extraction
When, the organic solvent for using is ether.
Embodiment 5
Embodiment 5 is with the difference of embodiment 3, and during ultrasonic extraction, solvent for use is 90% aqueous acetone solution.Extraction
When, the organic solvent for using is petroleum ether.
Embodiment 6
The structure of the benzisoxa furfuran compound that embodiment 1 is prepared is measured by the following method；The present invention
Compound is light yellow gum thing；HRESI-MS shows that its quasi-molecular ion peak is 255.0990 [M+Na]+(calculated value
255.0997), with reference to1H NMR and DEPT spectrum determine that its molecular formula is C14H16O3, degree of unsaturation is 7.Shown in infrared spectrum
Aromatic ring (1612,1568 and 1464cm-1) resonance absorbing peak.And ultraviolet spectra has absorption maximum also to say in 210,245,280nm
Aromatic ring structure is there may be in clear compound.Compound1H and13C H NMR spectroscopies (table 1) show that it contains 14 carbon and 16
Hydrogen, including 11,2,4,5- quaternary phenyl ring (C-4~C-7, C-4a and C-7a, H-7), 1 humorous dimethyl chromene ring (C-
1'~C-5', H-1', H-2' and H6- 4', 5'), two methylene (C-1 and C-3 of oxidation；H2- 1 and H2-3)；And 1 first
Epoxide (δC61.2；δH3.85).Its HMBC coherent signal is further analyzed, according to H2- 1 and C-3, C-4a, C-7, C-7a；H2-
3 and C-1, C-4, C-4a, C-7a；And H-7 (figure -3) related to the HMBC of C-1, C-4a, C-7a can speculate that compound is benzo
Different furans class formation.H-1' and C-4, C-5, C-6 can be observed in the HMBC spectrums of compound；H-2' and C-5, and H-4 and C-
The long-range correlation of 1', can speculate that humorous dimethyl chromene ring is substituted in C-5 and C-6 of compound, and C-1' carbon is connected to
C-5 of phenyl ring；Methoxy substitution can be by methoxyl group hydrogen (δ at C-4H3.85) with C-4 (δC156.3) HMBC is related
To determination.So far, the structure of compound determined, and is named as Compound nomenclature and is：6,8- dihydro -5- methoxyl groups -2,2-
Dimethyl -2H- furans [3,4-g] chromene.
Embodiment 7
Compound prepared by Example 2-5, is light yellow gum thing.Determine same as Example 6, confirm to implement 2-5
The compound of preparation is the benzisoxa furfuran compound --- 6,8- dihydro -5- methoxyl group -2,2- dimethyl -2H- furans
[3,4-g] chromene.
Embodiment 8
The benzisoxa furan compound of any preparation in Example 1-5 carries out the additive effect experiment of cigarette filter, examination
Test situation as follows：
For cigarette " purple cloud, " that addition cigarette is Hong Yun Red River group with triacetyl glycerine by above-mentioned benzisoxa furans
The compound solution for being made into 0.1mg/mL.Uniformly it is sprayed onto on filter tow by the 8% of filter tow weight, is made filter
Rod, is then made cigarette by the filter stick by conventional cigarette cigarette, carries out sensory evaluation, and to be not added with the phase of the compound
With cigarette as control.Evaluation and analysis result shows：Compared with control, the sweet sense of cigarette smoking is obviously improved, promotes the production of body fluid and feel protrusion,
Suction comfortableness be improved significantly, the results are shown in Table 2.
Embodiment 9
The benzisoxa furan compound of any preparation in Example 1-5 carries out the additive effect experiment of cigarette filter, examination
Test situation as follows：
For cigarette " purple cloud, " that addition cigarette is Hong Yun Red River group with triacetyl glycerine by above-mentioned benzisoxa furans
The compound solution for being made into 0.2mg/mL.Uniformly it is sprayed onto on filter tow by the 5% of filter tow weight, is made filter
Rod, is then made cigarette by the filter stick by conventional cigarette cigarette, carries out sensory evaluation, and to be not added with the phase of the compound
With cigarette as control.Evaluation and analysis result shows：Compared with control, the sweet sense of cigarette smoking is obviously improved, promotes the production of body fluid and feel protrusion,
Suction comfortableness be improved significantly, the results are shown in Table 2.
The cigarette sense organ Comfort Evaluation of table 2
Note：Fraction is higher, and product sensory quality is better.
General principle of the invention, principal character and advantages of the present invention has been shown and described above.The technology of the industry
Personnel it should be appreciated that the present invention is not limited to the above embodiments, simply explanation described in above-described embodiment and specification this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appending claims and its
Equivalent thereof.
Claims (8)
1. a kind of benzisoxa furfuran compound that can improve cigarette smoking effect, it is characterised in that the benzisoxa furans
Compound is isolated from tobacco, is named as：6,8- dihydro -5- methoxyl group -2,2- dimethyl -2H- furans [3,4-g ]
Chromene, English is entitled：6,8-dihydro-5- methoxy-2,2-dimethyl-2H-furo[3,4-g] chromene, its
Molecular formula is C14H16O3, structure such as formula（I）It is shown：
, formula（I）.
2. the preparation method of the benzisoxa furfuran compound of cigarette smoking effect can be improved described in a kind of claim 1, and it is special
Levy and be, with tobacco as raw material, through medicinal extract extraction, organic solvent extraction, MCI decolourings, silica gel column chromatography and high performance liquid chromatography
Separating step is obtained, specially：
A, medicinal extract are extracted：Tobacco is crushed to 20 ~ 40 mesh, 2 ~ 5 times are extracted with the solvent supersonics of 5 ~ 10 times of tobacco weight, every time 30
~ 60 minutes, merge extract solution and filter, filtrate decompression is concentrated into the 1/4 of original volume, stands, and sediment is filtered, afterwards by gained
Filtrate decompression is condensed into medicinal extract a；
B, organic solvent extraction：To the water that weight is 1 ~ 2 times of medicinal extract a weight is added in medicinal extract a, then have with isometric with water
Machine solvent extraction 3 ~ 5 times, merges organic solvent extraction phase, the organic solvent extraction phase for obtaining will be merged afterwards and is concentrated under reduced pressure into leaching
Cream b；
C, MCI decolourize：It is 50 ~ 100% methanol aqueous solutions to the volumetric concentration that addition in medicinal extract b is 3 ~ 5 times of medicinal extract b weight, waits to soak
After cream b is completely dissolved, upper MCI posts are that 90%-95% methanol aqueous solutions are eluted with volumetric concentration, merge eluent, afterwards will
Eluent after merging is concentrated under reduced pressure into medicinal extract c；
D, silica gel column chromatography：By silica gel column chromatography on medicinal extract c, dress post silica gel is 160 ~ 200 mesh, and consumption is medicinal extract c weight 6 ~ 10
Measure again；It is 1 with volume ratio:0~0:1 chloroform and acetone mixed organic solvents gradient elution, collects the gradient eluent of each gradient
And be concentrated under reduced pressure, monitored through TLC, merge identical part；
E, high performance liquid chromatography separation：It is 7 by volume ratio:The eluent that 3 chloroform-acetone is afforded, through high-efficient liquid phase color
Spectrum is isolated and purified, and obtains final product described benzisoxa furfuran compound.
3. the preparation method of the benzisoxa furfuran compound that can improve cigarette smoking effect according to claim 2, its
It is characterised by, the solvent of the step A is aqueous acetone solution, second that volumetric concentration be 90 ~ 100% of the volumetric concentration for 70 ~ 100%
Alcohol solution or the methanol aqueous solution that volumetric concentration is 90 ~ 100%.
4. the preparation method of the benzisoxa furfuran compound that can improve cigarette smoking effect according to claim 2, its
It is characterised by, the organic solvent of the step B is dichloromethane, chloroform, ethyl acetate, ether or petroleum ether.
5. the preparation method of the benzisoxa furfuran compound that can improve cigarette smoking effect according to claim 2, its
It is characterised by, medicinal extract c is the acetone or first of 1.5 ~ 3 times of medicinal extract c with weight before through silica gel column chromatography, first in the D steps
Alcohol dissolves, and is then 80 ~ 100 mesh silica gel mixed samples of 0.8 ~ 1.2 times of medicinal extract c with weight, afterwards loading.
6. the preparation method of the benzisoxa furfuran compound that can improve cigarette smoking effect according to claim 2, its
It is characterised by, in the D steps, during gradient elution, the chloroform and the volume ratio of acetone mixed organic solvents for being used are followed successively by
20:1、9:1、8:2、7:3、6:4 and 1:1, after each gradient elution to TLC point plates is without point, change next gradient elution.
7. the preparation method of the benzisoxa furfuran compound that can improve cigarette smoking effect according to claim 2, its
It is characterised by, it with 40% methyl alcohol is mobile phase, 15 ~ 25ml/ of flow velocity that the purifying of the high performance liquid chromatography separation of the E steps is
Min, with 21.2 × 250mm, 5 μm of Zorbax PrepHT GF reverse phase preparative columns are fixing phase, UV-detector Detection wavelength
It is 280nm, the μ L of each sample introduction 10 ~ 100 collect the chromatographic peak of 35.2min, are evaporated after repeatedly adding up.
8. the benzisoxa furfuran compound that can improve cigarette smoking effect described in claim 1 adds as cigarette filter is prepared
Plus the application of agent.
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