CN107778275A - A kind of isoflavonoid extracted in the waste residue from rose and its preparation method and application - Google Patents
A kind of isoflavonoid extracted in the waste residue from rose and its preparation method and application Download PDFInfo
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- CN107778275A CN107778275A CN201710971747.5A CN201710971747A CN107778275A CN 107778275 A CN107778275 A CN 107778275A CN 201710971747 A CN201710971747 A CN 201710971747A CN 107778275 A CN107778275 A CN 107778275A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/34—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 3 only
- C07D311/36—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 3 only not hydrogenated in the hetero ring, e.g. isoflavones
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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
- A24B3/00—Preparing tobacco in the factory
- A24B3/12—Steaming, curing, or flavouring tobacco
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Abstract
The invention discloses isoflavonoid extracted in a kind of waste residue from rose and its preparation method and application.Compound nomenclature is：4' hydroxyls 7 (3 hydroxypropanoyl) 6 methoxy isoflavones, English name：4'hydroxy 7 (3 hydroxypropanoyl) 6 methoxy isoflavone, its molecular formula C19H16O6, its structural formula：To produce the Damask Rose waste residue after Rosa Damascana as raw material, extract through medicinal extract, organic solvent extraction, MCI decolourize, be made after silica gel column chromatography and high performance liquid chromatography separation.The compounds of this invention is added in cigarette filter, can coordinate this perfume with tobacco, reduce the excitant of cigarette smoking, there is the obvious effect of promoting the production of body fluid and flue gas to return sweet effect, the positive effect of soft flue gas.
Description
Technical field
The invention belongs to technical field of phytochemistry, is specifically related to the Damask Rose after a kind of essential oil from production and gives up
Obtained isoflavonoid is extracted in slag first, the compound can improve the suction quality of cigarette.Meanwhile the present invention is also
It is related to the preparation method of the compound, and application of the compound in production of cigarettes.
Background technology
Damask Rose (scientific name Rosa Damascena, common first names Damask rose), also known as Tujue rose, rose
Section's Rosa, belong to classic garden rose, bush plant, originate in Syria, started in 14th century widely to plant in France, greatly
Ma Shige roses are also the main rose variety of Bulgaria's plantation, open hose-in-hose, petal edge color is slightly shallow, has as silks and satins
Texture；Purely, the careful fragrance of a flower makes its hat pressure beautiful and fragrant flowers, turns into the top grade in rose for oil, thus is widely cultivated to carry
Take Rosa Damascana.Rosa Damascana is the essential oil of most expensive in the world, is referred to as " after essential oil ".Except being widely used in food and change
Outside cosmetic, Rosa Damascana is also widely used in perfuming cigarette；There is cigarette after addition Rosa Damascana tobacco to add Rose Essentielle
Composite fragrant feature, jealous abundant sweetness, smoke is pure and fresh light refreshing, and unique enjoyment of graceful fragrance can be brought to consumer.
Rosa Damascana is usually using the fresh rose flower plucked in the morning as raw material, passes through distillation or the method for supercritical extract
Prepare, the yield of Rosa Damascana is extremely low, and the flower of about five tons of weights can only extract two pounds of attar of rose.Rose after essential oil generation
A large amount of chemical compositions with value of exploiting and utilizing are also rich in rare waste residue, such as：Quercitrin, amaroid, tannin, fat oil, have
Machine acid (gallic acid), haematochrome, uranidin, beta carotene etc..Rose waste residue after production essential oil is comprehensively utilized,
To comprehensively utilizing resource, the added value for improving rose processing has important practical significance.
Research shows, outside the routine chemical componentses such as isolating protein, amino acid, sugar, phosphorus, calcium, potassium, after producing Rosa Damascana
Also contain a large amount of secondary metabolites in rose waste residue, type of compounds includes flavones, cumarin, tannin, furans, flavones, benzene
C prime, terpene, alkaloid etc..These compounds have multiple biological activities, in antibacterial, anti-inflammatory, anti-mutation, decompression, heat-clearing solution
The many aspects such as poison, calmness, diuresis, anti-oxidant, anticancer, anti-cancer, suppression lipase have remarkable result.
Isoflavonoid, which refers to two, has the phenyl ring (A- and B- rings) of phenolic hydroxyl group mutual by central thricarbon atom
A series of compounds to link, its basic parent nucleus are 3- phenyl chromones.Often it is connected with isoflavonoid structure
The functional groups such as phenolic hydroxyl group, methoxyl group, methyl, isopentene group.In addition, it is also often combined into glycosides with sugar.The effect of isoflavones is more
Aspect, it is a kind of very strong antioxidant, and the ability for preventing oxidation is more than ten times of vitamin E, this antioxidation
Degeneration, the aging of cell can be prevented, can also prevent the generation of cancer.Isoflavones can improve blood circulation, reduce cholesterol,
Improve cardiovascular and cerebrovascular disease.In addition, isoflavonoid also has prominent improvement sense of taste effect, some isoflavonoids
Gustatory Representation it is very special, have a kind of natural sweet taste after entrance.Isoflavones contained by the root of kudzu vine be exactly its can return it is sweet main
Reason, and content is higher, returns sweet more obvious, and smell is more mellow.
A kind of present invention isolated isoflavonoid from the Damask Rose waste residue after production Rosa Damascana,
The compound and its application in production of cigarettes are there is not yet relevant report.
The content of the invention
It is an object of the invention to provide a kind of new isoflavonoid.
It is a further object to provide a kind of method for preparing the isoflavonoid.
The present invention also aims to provide application of the described isoflavonoid in flavor quality of cigarette is improved.
The purpose of the present invention is achieved by the following technical programs.
Unless otherwise indicated, percentage of the present invention is mass percent.
Obtained isoflavonoid, its point are extracted in a kind of Damask Rose waste residue after Rosa Damascana from production
Minor is C19H16O6, there is following structural formula：
The compound is orange-yellow jelly, is named as：4'- hydroxyls -7- (3- hydroxypropanoyls) -6- methoxyl groups-different Huang
Ketone, English are entitled：4'-hydroxy-7-(3-hydroxypropanoyl)-6-methoxy-isoflavone.
A kind of method for preparing the isoflavonoid, be to produce the rose waste residue after Rosa Damascana as raw material,
Extracted through medicinal extract, organic solvent extraction, MCI decolourizes, silica gel column chromatography and high performance liquid chromatography separation obtain, specifically include following
Step：
(1) medicinal extract extracts：Damask Rose waste residue powder after production Rosa Damascana is extracted 2~5 times with solvent supersonic,
30~60 minutes every time, the quality of each Extraction solvent used was 2~6 times of waste residue powder quality；Merge extract solution and filter, filter
Liquid, which is concentrated under reduced pressure into, just sediment precipitation, stands 20~60 minutes, filters out sediment, be afterwards condensed into gained filtrate decompression
Medicinal extract a；Described Extraction solvent is acetone, the ethanol or body of volumetric concentration 90%~100% of volumetric concentration 70%~100%
The methanol of product concentration 90%~100%；
(2) organic solvent extracts：The water of 1~2 times of weight is added into medicinal extract a, is then extracted 3~5 times with organic solvent,
The volume of organic solvent used is identical with the volume for adding water every time；Merge organic solvent extraction phase, be concentrated under reduced pressure into medicinal extract b；
Described organic solvent is dichloromethane, chloroform, ethyl acetate, ether or petroleum ether；
(3) MCI decolourizes：Into medicinal extract b, 3~5 times of weight of addition, volumetric concentration 95% methanol aqueous solution, treats medicinal extract b
Upper MCI posts after being completely dissolved, are eluted with the methanol aqueous solution that volumetric concentration is 90%~95%, and it is dense to merge eluent decompression
Shorten medicinal extract c into；
(4) silica gel column chromatography：Silica gel column chromatography on medicinal extract c, the mesh of dress post silica gel 160~200, silica gel dosage are medicinal extract c weights
6~10 times of amount；Gradient elution is carried out with chloroform-acetone solution, after each gradient elution to TLC point plates is without point, changed next
Gradient elution；Gradient eluent, concentration are collected, is monitored through TLC, merges identical part；The volume proportion of chloroform-acetone solution
Respectively 20:1、9:1、8:2、7:3、6:4 and 1:1；
(5) high performance liquid chromatography separation：By column chromatography eluent 7:3 part is purified using high performance liquid chromatography separation,
34.6min chromatographic peak is collected, is evaporated after repeatedly adding up, produces described isoflavonoid.
In step (4), before upper silica gel column chromatography, the acetone or methanol first measured with weight than 1.5~3 times dissolve medicinal extract c,
Then 80~100 mesh silica gel mixed samples of 0.8~2.0 times of medicinal extract c weight are used.
In step (5), the purifying of described high performance liquid chromatography separation is using the methanol aqueous solution of volumetric concentration 53% as stream
Dynamic phase, flow velocity 20ml/min, with 21.2 × 250mm, 5 μm of ZorbaxPrepHT GF reverse phase preparative columns are stationary phase, ultraviolet inspection
It is 358nm to survey device Detection wavelength, each μ L of sample introduction 50~200, collects 34.6min chromatographic peak, is evaporated after repeatedly adding up.
The present invention is unrestricted to the granularity of waste residue powder.
The structure of prepared compound is identified by the following method：
The compound is orange-yellow jelly, and HRESI-MS shows that its quasi-molecular ion peak is 363.0838 [M+Na]+(meter
Calculation value 363.0845), with reference to1H NMR and DEPT spectrum determine that its molecular formula is C19H16O6, degree of unsaturation 12.In infrared spectrum
Show hydroxyl (3421), carbonyl (1684 and 1652) and aromatic ring (1615,1557 and 1460cm-1) resonance absorbing peak.It is and purple
External spectrum there may be aromatic ring structure in 210,264,358nm have absorption maximum to also illustrate that compound.
Nuclear magnetic resonance data (500/125MHz, solvent CDCl of the compound of table -1 13)
Compound1H and13C H NMR spectroscopies data (such as table 1, Fig. 1 and 2) show that it contains 19 carbon and 16 hydrogen, including 1
Individual 1,2,4,5- quaternary phenyl ring (C-5~C-10, H-5, H-8), 1 Isosorbide-5-Nitrae-dibasic phenyl ring (C-1'~C-6', H-
2', 6' and H-3', 5'), 1 α, beta-unsaturated carbonyl (C-2, C-3, C-4, H-3), 13 hydroxypropanoyl (C-1 "~C-3 ",
H2- 2 " and H2- 3 "), 1 methoxyl group (δC56.3q δH3.84s), and 1 phenolic hydroxyl group (δH10.92s).According to typical 2
Individual phenyl ring, α, beta-unsaturated carbonyl signal, it is isoflavonoid that can speculate the compound.According to H-2 and C-3, C-4, C-
9th, C-1 ', H-5 and C-4, C-9, C-10, H-8 and C-6, C-7, C-9, C-10, and H-2', 6 ' it is related to C-3 HMBC (such as
Fig. 2) may further confirm that compound is osajin structure.After the parent of compound determines, remaining substituent, 3 hydroxyls third
Acyl group, methoxyl group and phenolic hydroxyl group can be considered the substituent on flavones.Methoxyl group can be observed in (such as Fig. 3) in the HMBC spectrums of compound
Hydrogen (δH3.84) with C-6 (δC155.0) HMBC is related, and the methoxy substitution can be speculated in C-6 positions；According to H2-2”(δH2.90) with C-7 (δC, and H-8 (δ 127.2)HAnd C-1 " (δ 6.70)C199.3) HMBC is related, it can be verified that 3 hydroxyls third
Acyl group is substituted in C-7 positions.Phenolic hydroxyl group is substituted in C-4' can be by phenolic hydroxyl group hydrogen (δHAnd C-3', 5'(δ 10.92)C115.9) and
C-4'(δC157.8) HMBC correlations are confirmed.Proton signal [H-5, δ on typical phenyl ring in additionH7.14s；H-8,δH6.70s；H-2 ', 6 ', δH7.76(d)8.8；H-3 ', 5 ', δH6.76 (d) 8.8] also the A rings of susceptible of proof compound be 6,7- positions
Two substitutions, B rings are that 4'- positions are monosubstituted.So far,
The structure of compound is determined, is named as：4'- hydroxyls -7- (3- hydroxypropanoyls) -6- methoxy-isofiavones.
Infrared, the ultraviolet and mass spectrometric data of compound：UV (methanol), λmax(logε)358(3.62),264(3.80),210
(4.42)nm；IR (pressing potassium bromide troche)：νmax3421、1684、1652、1615、1557、1460、1382、1156、1068cm-1；1H
With13C NMR datas (500 and 125MHz, (CDCl3), it is shown in Table -1；Positive ion mode ESIMS m/z363 [M+Na]+；Cation
Pattern HRESIMS m/z 363.0838 [M+Na]+(C19H16NaO6, calculated value 363.0845).
Described isoflavonoid is made into 0.5mg/mL solution with triacetyl glycerine.By filter tow weight
5-8% be uniformly sprayed onto on filter tow, filter stick is made, then by the filter stick and conventional cigarette cigarette, carries out sense organ and comments
Analysis, and the identical cigarette to be not added with the compound is used as control.Evaluation and analysis result shows：Compared with control, chemical combination of the present invention
Thing is added in cigarette filter, can coordinate this perfume with tobacco, reduce the excitant of cigarette smoking, have the obvious effect of promoting the production of body fluid
Sweet effect, the positive effect of soft flue gas are returned with flue gas.Therefore the compound can be used as prepare cigarette filter-tip additive agent answer
With.
Compared with prior art, beneficial effects of the present invention are：
1st, raw material is extracted as the waste residue after production Rosa Damascana, and source is very extensive, and cost is low；The discarded money of comprehensive utilization
Source, it is remarkably improved the added value of rose processing.
2nd, the compounds of this invention is simple in construction, can also be produced by artificial synthesized, be easier to realize, carried for tobacco industry
For new additive.The compound dissolves in triacetyl glycerine, is added in cigarette filter forming process, is not required to increase
Extra process, it is easy to utilize.
3rd, the compounds of this invention is added in cigarette filter, can coordinates this perfume with tobacco, reduce the thorn of cigarette smoking
Swash property, there is the obvious effect of promoting the production of body fluid and flue gas to return sweet effect, the positive effect of soft flue gas.
Brief description of the drawings
Fig. 1 be isoflavonoid of the present invention carbon-13 nmr spectra (13C NMR)；
Fig. 2 be isoflavonoid of the present invention proton nmr spectra (1H NMR)；
Fig. 3 is the related figures of crucial HMBC of isoflavonoid of the present invention.
Embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples, but drawings and examples are not pair
The restriction of technical solution of the present invention, it is all based on present invention teach that made change or equivalent substitution, all should belong to the present invention
Protection domain.
In the examples where no specific technique or condition is specified, carried out according to routine techniques in the art or condition, or
Carried out according to product description.Material therefor or the unreceipted production firm person of equipment, being can be by buying the routine obtained
Product.
Embodiment 1
The waste residue sample source after Rosa Damascana is produced in Yunnan Yuxi, kind is Damask Rose.
A, medicinal extract extracts：Waste residue powder after production Rosa Damascana is extracted 2 times with solvent supersonic, every time Extraction solvent used
Quality be 2 times of waste residue powder quality, each extraction time is 30 minutes, merges extract solution and simultaneously filters, filtrate decompression is concentrated into
Just there is sediment precipitation, stand 20 minutes, filter out sediment, gained filtrate decompression is condensed into medicinal extract a afterwards；
B, organic solvent extracts：The water that weight is 1 times of medicinal extract a weight is added into medicinal extract a, is then extracted with organic solvent
3 times, the volume of organic solvent used is identical with water volume every time, merges organic solvent extraction phase, will merge what is obtained afterwards
Organic solvent extraction phase is concentrated under reduced pressure into medicinal extract b；
C, MCI decolourizes：Into medicinal extract b, addition is that the volumetric concentration of 3 times of medicinal extract b weight is 95% methanol aqueous solution, waits to soak
After cream b is completely dissolved, upper MCI posts, it is that 90% methanol aqueous solution is eluted with volumetric concentration, merges eluent, will close afterwards
Eluent after and is concentrated under reduced pressure into medicinal extract c；
D, silica gel column chromatography：Medicinal extract c is first that 1.5 times of medicinal extract c acetone or methanol dissolve with weight, then uses weight
It is 0.8 times of medicinal extract c 80 mesh silica gel mixed samples, loading carries out column chromatography afterwards, and dress post silica gel is 160 mesh, the weight of used silica gel
For 6 times of amounts of medicinal extract c weight；Using volume ratio as 20:1、9:1、8:2、7:3、6:4 and 1:1 chloroform and acetone mixed organic solvents
Gradient elution, after each gradient elution to TLC point plates is without point, change next gradient elution；Collect the gradient eluent of each gradient
And concentrate, monitored through TLC, merge identical part；
E, high performance liquid chromatography separation：Volume ratio will be used as 7:3 chloroform-acetone mixed organic solvents afford
Part is purified using high performance liquid chromatography separation, and the specific method of high performance liquid chromatography separation purifying is：Using volumetric concentration as
53% methanol aqueous solution is mobile phase, and flow velocity 20ml/min, with 21.2 × 250mm, 5 μm of ZorbaxPrepHT GF are anti-phase
It is stationary phase to prepare post, and UV-detector Detection wavelength is 358nm, each μ L of sample introduction 50, collects 34.6min chromatographic peak, more
It is secondary it is cumulative after be evaporated, produce described isoflavonoid.
Wherein, the solvent of step A is the aqueous acetone solution that volumetric concentration is 70%.The organic solvent of the step B is chlorine
It is imitative.
Embodiment 2
The waste residue sample source after Rosa Damascana is produced in Yunnan Yuxi, kind is Damask Rose.
A, medicinal extract extracts：Waste residue powder after production Rosa Damascana is extracted 5 times with solvent supersonic, every time Extraction solvent used
Quality be 6 times of waste residue powder quality, each extraction time is 60 minutes, merges extract solution and simultaneously filters, filtrate decompression is concentrated into
Just there is sediment precipitation, stand 60 minutes, filter out sediment, gained filtrate decompression is condensed into medicinal extract a afterwards；
B, organic solvent extracts：The water that weight is 2 times of medicinal extract a weight is added into medicinal extract a, is then extracted with organic solvent
5 times, the volume of organic solvent used is identical with water volume every time, merges organic solvent extraction phase, will merge what is obtained afterwards
Organic solvent extraction phase is concentrated under reduced pressure into medicinal extract b；
C, MCI decolourizes：Into medicinal extract b, addition is that the volumetric concentration of 5 times of medicinal extract b weight is 95% methanol aqueous solution, waits to soak
After cream b is completely dissolved, upper MCI posts, it is that 95% methanol aqueous solution is eluted with volumetric concentration, merges eluent, will close afterwards
Eluent after and is concentrated under reduced pressure into medicinal extract c；
D, silica gel column chromatography：Medicinal extract c is first that 3 times of medicinal extract c acetone or methanol dissolve with weight, is then with weight
1.2 times of medicinal extract c 100 mesh silica gel mixed samples, afterwards loading carry out column chromatography, dress post silica gel is 200 mesh, the weight of used silica gel
For 10 times of amounts of medicinal extract c weight；Using volume ratio as 20:1、9:1、8:2、7:3、6:4 and 1:1 chloroform and acetone mixed organic solvents
Gradient elution, after each gradient elution to TLC point plates is without point, change next gradient elution；Collect the gradient eluent of each gradient
And concentrate, monitored through TLC, merge identical part；
E, high performance liquid chromatography separation：Volume ratio will be used as 7:3 chloroform-acetone mixed organic solvents afford
Part is purified using high performance liquid chromatography separation, and the specific method of high performance liquid chromatography separation purifying is：Using volumetric concentration as
53% methanol aqueous solution is mobile phase, and flow velocity 20ml/min, with 21.2 × 250mm, 5 μm of ZorbaxPrepHT GF are anti-phase
It is stationary phase to prepare post, and UV-detector Detection wavelength is 358nm, each μ L of sample introduction 200, collects 34.6min chromatographic peak, more
It is secondary it is cumulative after be evaporated, produce described isoflavonoid.
Wherein, the solvent of step A is acetone.The organic solvent of the step B is dichloromethane.
Embodiment 3
The waste residue sample source after Rosa Damascana is produced in Yunnan Yuxi, kind is Damask Rose.
A, medicinal extract extracts：Waste residue powder after production Rosa Damascana is extracted 3 times with solvent supersonic, every time Extraction solvent used
Quality be 3 times of waste residue powder quality, each extraction time is 40 minutes, merges extract solution and simultaneously filters, filtrate decompression is concentrated into
Just there is sediment precipitation, stand 40 minutes, filter out sediment, gained filtrate decompression is condensed into medicinal extract a afterwards；
B, organic solvent extracts：The water that weight is 1.5 times of medicinal extract a weight is added into medicinal extract a, is then extracted with organic solvent
Take 4 times, the volume of organic solvent used is identical with water volume every time, merges organic solvent extraction phase, afterwards obtains merging
Organic solvent extraction phase be concentrated under reduced pressure into medicinal extract b；
C, MCI decolourizes：Into medicinal extract b, addition is that the volumetric concentration of 4 times of medicinal extract b weight is 95% methanol aqueous solution, waits to soak
After cream b is completely dissolved, upper MCI posts, it is that 93% methanol aqueous solution is eluted with volumetric concentration, merges eluent, will close afterwards
Eluent after and is concentrated under reduced pressure into medicinal extract c；
D, silica gel column chromatography：Medicinal extract c is first that 2 times of medicinal extract c acetone or methanol dissolve with weight, is then with weight
1 times of medicinal extract c 90 mesh silica gel mixed samples, the column chromatography of loading progress afterwards, dress post silica gel are 180 mesh, and the weight of used silica gel is leaching
8 times of amounts of cream c weight；Using volume ratio as 20:1、9:1、8:2、7:3、6:4 and 1:1 chloroform and acetone mixed organic solvents gradient
Elution, after each gradient elution to TLC point plates is without point, changes next gradient elution；Collect the gradient eluent of each gradient and dense
Contracting, is monitored through TLC, merges identical part；
E, high performance liquid chromatography separation：Volume ratio will be used as 7:3 chloroform-acetone mixed organic solvents afford
Part is purified using high performance liquid chromatography separation, and the specific method of high performance liquid chromatography separation purifying is：Using volumetric concentration as
53% methanol aqueous solution is mobile phase, and flow velocity 20ml/min, with 21.2 × 250mm, 5 μm of ZorbaxPrepHT GF are anti-phase
It is stationary phase to prepare post, and UV-detector Detection wavelength is 358nm, each μ L of sample introduction 100, collects 34.6min chromatographic peak, more
It is secondary it is cumulative after be evaporated, produce described isoflavonoid.
Wherein, the solvent of step A is ethanol.The organic solvent of the step B is ethyl acetate.
The present embodiment uses waste residue powder 4.4kg, obtains medicinal extract a120g, medicinal extract b80g, medicinal extract c62g, volume ratio 7:3
The part 18g that chloroform-acetone mixed organic solvents afford.
Embodiment 4
The waste residue sample source after Rosa Damascana is produced in hotan, kind is Damask Rose.
A, medicinal extract extracts：Waste residue powder after production Rosa Damascana is extracted 4 times with solvent supersonic, every time Extraction solvent used
Quality be 4 times of waste residue powder quality, each extraction time is 50 minutes, merges extract solution and simultaneously filters, filtrate decompression is concentrated into
Just there is sediment precipitation, stand 40 minutes, filter out sediment, gained filtrate decompression is condensed into medicinal extract a afterwards；
B, organic solvent extracts：The water that weight is 1.2 times of medicinal extract a weight is added into medicinal extract a, is then extracted with organic solvent
Take 4 times, the volume of organic solvent used is identical with water volume every time, merges organic solvent extraction phase, afterwards obtains merging
Organic solvent extraction phase be concentrated under reduced pressure into medicinal extract b；
C, MCI decolourizes：Into medicinal extract b, addition is that the volumetric concentration of 4.5 times of medicinal extract b weight is 95% methanol aqueous solution, is treated
After medicinal extract b is completely dissolved, upper MCI posts, it is that 92% methanol aqueous solution is eluted with volumetric concentration, merges eluent, afterwards will
Eluent after merging is concentrated under reduced pressure into medicinal extract c；
D, silica gel column chromatography：Medicinal extract c is first that 2.5 times of medicinal extract c acetone or methanol dissolve with weight, then uses weight
It is 0.9 times of medicinal extract c 80 mesh silica gel mixed samples, loading carries out column chromatography afterwards, and dress post silica gel is 160 mesh, the weight of used silica gel
For 8 times of amounts of medicinal extract c weight；Using volume ratio as 20:1、9:1、8:2、7:3、6:4 and 1:1 chloroform and acetone mixed organic solvents
Gradient elution, after each gradient elution to TLC point plates is without point, change next gradient elution；Collect the gradient eluent of each gradient
And concentrate, monitored through TLC, merge identical part；
E, high performance liquid chromatography separation：Volume ratio will be used as 7:3 chloroform-acetone mixed organic solvents afford
Part is purified using high performance liquid chromatography separation, and the specific method of high performance liquid chromatography separation purifying is：Using volumetric concentration as
53% methanol aqueous solution is mobile phase, and flow velocity 20ml/min, with 21.2 × 250mm, 5 μm of ZorbaxPrepHT GF are anti-phase
It is stationary phase to prepare post, and UV-detector Detection wavelength is 358nm, each μ L of sample introduction 80, collects 34.6min chromatographic peak, more
It is secondary it is cumulative after be evaporated, produce described isoflavonoid.
Wherein, the solvent of step A is methanol.The organic solvent of the step B is ether.
The present embodiment uses waste residue powder 10kg, obtains medicinal extract a 350g, medicinal extract b 210g, medicinal extract c 150g, and volume ratio is
7:The part 55g that 3 chloroform-acetone mixed organic solvents afford.
Embodiment 5
The waste residue sample source after Rosa Damascana is produced in hotan, kind is Damask Rose.
A, medicinal extract extracts：Waste residue powder after production Rosa Damascana is extracted 4 times with solvent supersonic, every time Extraction solvent used
Quality be 5 times of waste residue powder quality, each extraction time is 35 minutes, merges extract solution and simultaneously filters, filtrate decompression is concentrated into
Just there is sediment precipitation, stand 55 minutes, filter out sediment, gained filtrate decompression is condensed into medicinal extract a afterwards；
B, organic solvent extracts：The water that weight is 1.6 times of medicinal extract a weight is added into medicinal extract a, is then extracted with organic solvent
Take 4 times, the volume of organic solvent used is identical with water volume every time, merges organic solvent extraction phase, afterwards obtains merging
Organic solvent extraction phase be concentrated under reduced pressure into medicinal extract b；
C, MCI decolourizes：Into medicinal extract b, addition is that the volumetric concentration of 4.5 times of medicinal extract b weight is 95% methanol aqueous solution, is treated
After medicinal extract b is completely dissolved, upper MCI posts, it is that 94% methanol aqueous solution is eluted with volumetric concentration, merges eluent, afterwards will
Eluent after merging is concentrated under reduced pressure into medicinal extract c；
D, silica gel column chromatography：Medicinal extract c is first that 2.4 times of medicinal extract c acetone or methanol dissolve with weight, then uses weight
It is 1 times of medicinal extract c 100 mesh silica gel mixed samples, loading carries out column chromatography afterwards, and dress post silica gel is 200 mesh, the weight of used silica gel
For 7 times of amounts of medicinal extract c weight；Using volume ratio as 20:1、9:1、8:2、7:3、6:4 and 1:1 chloroform and acetone mixed organic solvents
Gradient elution, after each gradient elution to TLC point plates is without point, change next gradient elution；Collect the gradient eluent of each gradient
And concentrate, monitored through TLC, merge identical part；
E, high performance liquid chromatography separation：Volume ratio will be used as 7:3 chloroform-acetone mixed organic solvents afford
Part is purified using high performance liquid chromatography separation, and the specific method of high performance liquid chromatography separation purifying is：Using volumetric concentration as
53% methanol aqueous solution is mobile phase, and flow velocity 20ml/min, with 21.2 × 250mm, 5 μm of ZorbaxPrepHT GF are anti-phase
It is stationary phase to prepare post, and UV-detector Detection wavelength is 358nm, each μ L of sample introduction 120, collects 34.6min chromatographic peak, more
It is secondary it is cumulative after be evaporated, produce described isoflavonoid.
Wherein, the solvent of step A is the methanol aqueous solution that volumetric concentration is 95%.The organic solvent of the step B is stone
Oily ether.
Embodiment 6
The structure for the isoflavonoid being prepared using the method for embodiment 1 is measured by the following method：
The compound is orange-yellow jelly, and HRESI-MS shows that its quasi-molecular ion peak is 363.0838 [M+Na]+(meter
Calculation value 363.0845), with reference to1H NMR and DEPT spectrum determine that its molecular formula is C19H16O6, degree of unsaturation 12.In infrared spectrum
Show hydroxyl (3421), carbonyl (1684 and 1652) and aromatic ring (1615,1557 and 1460cm-1) resonance absorbing peak.It is and purple
External spectrum there may be aromatic ring structure in 210,264,358nm have absorption maximum to also illustrate that compound.
Compound1H and13C H NMR spectroscopies data (such as table 1, Fig. 1 and Fig. 2) show that it contains 19 carbon and 16 hydrogen, including
11,2,4,5- quaternary phenyl ring (C-5~C-10, H-5, H-8), 1 Isosorbide-5-Nitrae-dibasic phenyl ring (C-1'~C-6', H-
2', 6' and H-3', 5'), 1 α, beta-unsaturated carbonyl (C-2, C-3, C-4, H-3), 13 hydroxypropanoyl (C-1 "~C-3 ",
H2- 2 " and H2- 3 "), 1 methoxyl group (δC56.3q δH3.84s), and 1 phenolic hydroxyl group (δH10.92s).According to typical 2
Individual phenyl ring, α, beta-unsaturated carbonyl signal, it is isoflavonoid that can speculate the compound.According to H-2 and C-3, C-4, C-
9th, C-1 ', H-5 and C-4, C-9, C-10, H-8 and C-6, C-7, C-9, C-10, and H-2', 6 ' it is related to C-3 HMBC (such as
Fig. 2) may further confirm that compound is osajin structure.After the parent of compound determines, remaining substituent, 3 hydroxyls third
Acyl group, methoxyl group and phenolic hydroxyl group can be considered the substituent on flavones.Methoxyl group can be observed in (such as Fig. 3) in the HMBC spectrums of compound
Hydrogen (δH3.84) with C-6 (δC155.0) HMBC is related, and the methoxy substitution can be speculated in C-6 positions；According to H2-2”(δH2.90) with C-7 (δC, and H-8 (δ 127.2)HAnd C-1 " (δ 6.70)C199.3) HMBC is related, it can be verified that 3 hydroxyls third
Acyl group is substituted in C-7 positions.Phenolic hydroxyl group is substituted in C-4' can be by phenolic hydroxyl group hydrogen (δHAnd C-3', 5'(δ 10.92)C115.9) and
C-4'(δC157.8) HMBC correlations are confirmed.Proton signal [H-5, δ on typical phenyl ring in additionH7.14s；H-8,δH6.70s；H-2 ', 6 ', δH7.76(d)8.8；H-3 ', 5 ', δH6.76 (d) 8.8] also the A rings of susceptible of proof compound be 6,7- positions
Two substitutions, B rings are that 4'- positions are monosubstituted.So far, the structure of compound is determined, and is named as：4'- hydroxyls -7- (3- hydroxyls
Propiono) -6- methoxy-isofiavones.
Embodiment 7
Compound prepared by Example 2-5, is orange-yellow jelly.Assay method is same as Example 6, confirms to implement
Compound prepared by example 2-5 is the isoflavonoid --- 4'- hydroxyls -7- (3- hydroxypropanoyls) -6- methoxyl groups-different
Flavones.
Embodiment 8
The isoflavonoid of any preparation in Example 1-5 carries out the additive effect experiment of cigarette filter, experiment
Situation is as follows：
For the cigarette " purple cloud " that addition cigarette is Hong Yun Red River group, with triacetyl glycerine by above-mentioned osajin
Compound is made into 0.5mg/mL solution.Uniformly it is sprayed onto by the 8% of filter tow weight on filter tow, filter stick is made, so
The filter stick is subjected to sensory evaluation by being made cigarette with the cigarette cigarette of routine afterwards, and to be not added with the identical of the compound
Cigarette is as control.Evaluation and analysis result shows：The compounds of this invention can be coordinated this perfume with tobacco, can reduce the stimulation of cigarette smoking
Property, there is the obvious effect of promoting the production of body fluid, flue gas returns sweet effect and the positive effect of soft flue gas.
Embodiment 9
The isoflavonoid of any preparation in Example 1-5 carries out the additive effect experiment of cigarette filter：
For the cigarette " Camellia is soft " that addition cigarette is Hong Yun Red River group, with triacetyl glycerine by above-mentioned isoflavones
Class compound is made into 0.5mg/mL solution.Uniformly it is sprayed onto by the 5% of filter tow weight on filter tow, filter is made
Rod, cigarette then is made by the cigarette cigarette of routine in the filter stick, carries out sensory evaluation, and to be not added with the phase of the compound
With cigarette as control.Evaluation and analysis result shows：The compounds of this invention can be coordinated this perfume with tobacco, can reduce the thorn of cigarette smoking
Swash property, there is the obvious effect of promoting the production of body fluid, flue gas returns sweet effect and the positive effect of soft flue gas.
Claims (7)
1. a kind of isoflavonoid, its molecular formula is C19H16O6, there is following structural formula：
The Compound nomenclature is：4'- hydroxyls -7- (3- hydroxypropanoyls) -6- methoxy-isofiavones, English name：4'-
hydroxy-7-(3-hydroxypropanoyl)-6-methoxy-isoflavone。
2. preparing the method for isoflavonoid described in claim 1, following steps are specifically included：
(1) medicinal extract extracts：By produce Rosa Damascana after Damask Rose waste residue powder with solvent supersonic extract 2~5 times, every time
30~60 minutes, the quality of each Extraction solvent used was 2~6 times of waste residue powder quality；Merge extract solution and filter, filtrate subtracts
Pressure, which is concentrated into, just sediment precipitation, stands 20~60 minutes, filters out sediment, gained filtrate decompression is condensed into medicinal extract afterwards
a；Described Extraction solvent is the acetone of volumetric concentration 70%~100%, the ethanol of volumetric concentration 90%~100% or volume are dense
The methanol of degree 90%~100%；
(2) organic solvent extracts：Into medicinal extract a add 1~2 times of weight water, then with organic solvent extract 3~5 times, every time
The volume of organic solvent used is identical with the volume for adding water；Merge organic solvent extraction phase, be concentrated under reduced pressure into medicinal extract b；It is described
Organic solvent be dichloromethane, chloroform, ethyl acetate, ether or petroleum ether；
(3) MCI decolourizes：Into medicinal extract b, 3~5 times of weight of addition, volumetric concentration 95% methanol aqueous solution, treats that medicinal extract b is complete
Upper MCI posts after dissolving, are eluted with the methanol aqueous solution that volumetric concentration is 90%~95%, are merged eluent and are concentrated under reduced pressure into
Medicinal extract c；
(4) silica gel column chromatography：Silica gel column chromatography on medicinal extract c, the mesh of dress post silica gel 160~200, silica gel dosage is the 6 of medicinal extract c weight
~10 times；Gradient elution is carried out with chloroform-acetone solution, after each gradient elution to TLC point plates is without point, next gradient is changed and washes
It is de-；Gradient eluent, concentration are collected, is monitored through TLC, merges identical part；The volume proportion of the chloroform-acetone solution point
Wei 20:1、9:1、8:2、7:3、6:4 and 1:1；
(5) high performance liquid chromatography separation：By column chromatography eluent 7:3 part is purified using high performance liquid chromatography separation, is collected
34.6min chromatographic peak, it is evaporated after repeatedly adding up, produces described isoflavonoid.
3. preparation method according to claim 2, it is characterised in that：In step (4), medicinal extract c before upper silica gel column chromatography,
First dissolved with acetone or methanol of the weight than 1.5~3 times of amounts, then with 80~100 mesh silica gel of 0.8~2.0 times of medicinal extract c weight
Mix sample.
4. preparation method according to claim 2, it is characterised in that：In step (5), described high performance liquid chromatography separation
Purifying is the flow velocity 20ml/min using the methanol aqueous solution of volumetric concentration 53% as mobile phase, with 21.2 × 250mm, 5 μm
ZorbaxPrepHT GF reverse phase preparative columns are stationary phase, and UV-detector Detection wavelength is 358nm, each μ of sample introduction 50~200
L, 34.6min chromatographic peak is collected, be evaporated after repeatedly adding up.
5. application of the isoflavonoid in flavor quality of cigarette is improved described in claim 1.
6. application of the isoflavonoid described in claim 1 in cigarette filter-tip additive agent is prepared.
7. application of the isoflavonoid according to claim 6 in cigarette filter-tip additive agent is prepared, its feature exist
In：Described isoflavonoid is made into 0.5mg/mL solution, then the 5-8% by tow weight with triacetyl glycerine
Equably it is sprayed onto on cigarette filter tow, routinely filter stick is made in technique.
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| CN102796066A (en) * | 2012-08-31 | 2012-11-28 | 云南民族大学 | Flavone compound and preparation method and application thereof |
| US20170107242A1 (en) * | 2014-03-24 | 2017-04-20 | Institut National De La Recherche Agronomique | Novel flavonoids o-a-glucosylated on the b cycle, method for the production thereof and uses |
| CN107118194A (en) * | 2017-06-02 | 2017-09-01 | 云南中烟工业有限责任公司 | A kind of isoflavonoid that can improve cigarette smoking throat comfortableness and preparation method and application |
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| CN102796066A (en) * | 2012-08-31 | 2012-11-28 | 云南民族大学 | Flavone compound and preparation method and application thereof |
| US20170107242A1 (en) * | 2014-03-24 | 2017-04-20 | Institut National De La Recherche Agronomique | Novel flavonoids o-a-glucosylated on the b cycle, method for the production thereof and uses |
| CN107118194A (en) * | 2017-06-02 | 2017-09-01 | 云南中烟工业有限责任公司 | A kind of isoflavonoid that can improve cigarette smoking throat comfortableness and preparation method and application |
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| CN107903235A (en) * | 2017-12-15 | 2018-04-13 | 云南中烟工业有限责任公司 | A kind of isoflavone compound in rose waste residue and preparation method and application |
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