CN107400107B - Flavonoid compound in rose waste residue and preparation method and application thereof - Google Patents
Flavonoid compound in rose waste residue and preparation method and application thereof Download PDFInfo
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- 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
- C07D311/28—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 2 only
- C07D311/30—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 2 only not hydrogenated in the hetero ring, e.g. flavones
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- 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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- 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
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Abstract
The invention relates to a flavonoid compound in rose waste residue and a preparation method and application thereof, belonging to the technical field of phytochemistry. The flavonoid compound is separated from waste residue after the rose essential oil is produced by a distillation method, and the compound is named as: 5-hydroxy-2',7-dimethoxy-6-methyl-flavone with molecular formula C18H16O5The structural formula is shown as the formula (I):
formula (I); the preparation method takes waste residue after the production of the rose essential oil as a raw material and comprises the steps of extract extraction, organic solvent extraction, MCI decoloration, silica gel column chromatography and high performance liquid chromatography separation. The compound of the invention is added into cigarette filters, can coordinate with the original fragrance of tobacco, increases the sweet feeling of smoke, relieves the stimulation of the throat after smoking, has obvious effects of clearing and benefiting the throat and can improve the smoking quality of cigarettes.
Description
Technical Field
The invention belongs to the technical field of phytochemistry, relates to a flavonoid compound in rose waste residue, and a preparation method and application thereof, and particularly relates to a flavonoid compound extracted from waste residue after rose essential oil production for the first time. The compound is added into cigarette filter tip, can coordinate with tobacco essence, relieve throat irritation after smoking, has obvious effects of clearing heat from throat and benefiting throat, and can improve smoking quality of cigarette.
Background
Damascus rose (academic name)Rosa DamascenaThe Damask rose is commonly named as Damask rose), also named as jujuan rose, belongs to the rose in the rosaceous family, belongs to the classical garden, and is a bushy plant which is native to syria and is widely planted in france from the beginning of the 14 th century, and the Damask rose is a main rose variety planted in bulgaria, and has the characteristics of petal opening, light color of petal edge and silk-satin texture; the pure and fine floral fragrance makes it crown-like to be a top grade in oil roses, and is therefore widely planted for extracting essential oils from roses. Rose essential oil is the most expensive essential oil in the world and is called "after essential oil". Besides being widely applied to foods and cosmetics, the rose essential oil is also widely applied to cigarette flavoring; the cigarette added with the rose essential oil has the characteristic of composite fragrance of the tobacco and the rose, is rich and sweet in taste, fresh and light in smoke flavor, and can bring elegant and fragrant unique enjoyment to consumers.
The rose essential oil is prepared by taking fresh rose flowers picked in the morning as a raw material through a distillation or supercritical extraction method, the yield of the rose essential oil is extremely low, about five tons of heavy flowers can only extract two pounds of rose oil, and the waste residue generated by the essential oil is also rich in a large amount of chemical components with development and utilization values, such as quercitrin, bitter substances, tannin, fatty oil, organic acid (gallic acid), haematochrome, uranidin, β -carotene and the like.
Research shows that besides conventional chemical components such as protein, amino acid, sugar, phosphorus, calcium, potassium and the like, the waste residue after the rose essential oil is produced also contains a large amount of secondary metabolites, and the types of the compounds comprise flavone, coumarin, tannin, furan, flavone, phenylpropanoid, terpenoids, alkaloid and the like. The compounds have various biological activities and have remarkable effects in multiple aspects such as antibiosis, antiphlogosis, anti-mutation, blood pressure reduction, heat clearing and detoxifying, sedation, diuresis, antioxidation, anticancer, cancer prevention, lipase inhibition and the like.
The flavonoids generally refer to a series of compounds in which two benzene rings (A-and B-rings) having phenolic hydroxyl groups are connected with each other through a central three-carbon atom, and the basic nucleus of the compounds is 2-phenylchromone. The structure of the flavonoid compound is often connected with functional groups such as phenolic hydroxyl, methoxyl, methyl, isopentenyl and the like. In addition, it is often combined with a sugar to form a glycoside. The flavone has various effects, is a strong antioxidant, has oxidation prevention capability more than ten times of that of vitamin E, and can prevent cell degeneration, aging and cancer. The flavone has effects of improving blood circulation, reducing cholesterol, and improving cardiovascular and cerebrovascular diseases. In addition, the flavonoids have outstanding effect of improving the taste, some flavonoids have very special taste performance, and have natural sweet taste after being taken. The flavone contained in the olive is the main reason for returning the sweet taste, and the higher the flavone content is, the more obvious the returning sweet taste is, and the more mellow the smell is. The flavonoid compound is separated from the rose essential oil production waste residue, and the flavonoid compound can be added into the cigarette filter tip, so that the sweetness of smoke can be remarkably increased, the throat irritation after smoking is relieved, and the effect of improving the smoking quality of cigarettes is achieved.
Disclosure of Invention
The first purpose of the invention is to provide a flavonoid compound in rose waste residue; the second purpose is to provide a preparation method of the flavonoid compound; the third purpose is to provide the application of the flavonoid compound in flavoring the cigarette filter, which is used for increasing the sweet feeling of smoke, relieving the stimulation of the throat after smoking and improving the smoking quality of the cigarette.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the first purpose of the invention is realized by that the flavonoid compound in the rose waste residue is separated from the waste residue after the production of rose essential oil and is named as: 5-hydroxy-2',7-dimethoxy-6-methyl-flavone, english name: 5-hydroxy-2', 7-dimethoxy-6-methyl-flavanone with molecular formula C18H16O5The structural formula is shown as the formula (I):
The compound was a pale yellow gum, designated: the compound was named: 5-hydroxy-2',7-dimethoxy-6-methyl-flavone, english name: 5-hydroxy-2', 7-dimethoxy-6-methyl-flavanone.
The second purpose of the invention is realized by adopting the preparation method of the flavonoid compound, which is prepared by taking waste residue after the production of the rose essential oil as a raw material and carrying out the steps of extract extraction, organic solvent extraction, MCI decoloration, silica gel column chromatography and high performance liquid chromatography separation, and specifically comprises the following steps:
A. extracting the extractum: ultrasonically extracting the waste residue powder after the rose essential oil is produced for 2-5 times by using a solvent, wherein the mass of the extraction solvent used each time is 2-6 times of that of the waste residue powder, the extraction time is 30-60 minutes each time, combining the extracting solutions, filtering, concentrating the filtrate under reduced pressure until just precipitates are separated out, standing for 20-60 minutes, filtering out the precipitates, and then concentrating the obtained filtrate under reduced pressure to obtain an extract a;
B. organic solvent extraction: adding water with the weight 1-2 times that of the extract a into the extract a, extracting for 3-5 times by using an organic solvent, combining organic solvent extraction phases, and then concentrating the combined organic solvent extraction phases under reduced pressure to obtain an extract b, wherein the volume of the organic solvent used in each time is the same as that of the water;
C. MCI decoloration: adding a 95% methanol aqueous solution with volume concentration which is 3-5 times of the weight of the extract b into the extract b, loading the extract b on an MCI (methanol-to-oil) column after the extract b is completely dissolved, eluting by using a 90-95% methanol aqueous solution, merging the eluents, and then concentrating the merged eluents under reduced pressure to obtain an extract c;
D. silica gel column chromatography: performing silica gel column chromatography on the extract c, wherein the silica gel filled in the column is 160-200 meshes, and the weight of the silica gel is 6-10 times that of the extract c; performing gradient elution by using a chloroform-acetone mixed organic solvent with a volume ratio of 1: 0-0: 1, and replacing the next gradient elution after each gradient elution is performed until no point exists on a TLC spot plate; collecting gradient eluates of each gradient, concentrating, monitoring by TLC, and mixing the same fractions;
E. high performance liquid chromatography separation: and (3) separating and purifying the part eluted by the chloroform-acetone mixed organic solvent with the volume ratio of 6:4 by adopting high performance liquid chromatography to obtain the flavonoid compound.
Preferably, the solvent in step a is an acetone aqueous solution with a volume concentration of 70-100%, an ethanol aqueous solution with a volume concentration of 90-100%, or a methanol aqueous solution with a volume concentration of 90-100%.
Further, it is preferable that the organic solvent of the step B is dichloromethane, chloroform, ethyl acetate, diethyl ether or petroleum ether.
Further, preferably, in the step D, before the extract c is subjected to silica gel column chromatography, acetone or methanol with the weight 1.5-3 times that of the extract c is used for dissolving the extract c, then 80-100 mesh silica gel with the weight 0.8-1.2 times that of the extract c is used for mixing samples, and then the samples are loaded.
Further, in the step D, it is preferable that the chloroform-acetone mixed organic solvent used in the gradient elution has a volume ratio of 20:1, 9:1, 8:2, 7:3, 6:4 and 1:1 in this order; after each gradient eluted to the point where the TLC spot plate was no longer spotted, the next gradient elution was changed.
Further, preferably, the high performance liquid chromatography separation and purification of the step E is performed by taking a 40% methanol aqueous solution as a mobile phase, flowing at a rate of 15-25 ml/min, using a 21.2 × 250mm, 5 μm Zorbax PrepHT GF reverse phase preparative column as a stationary phase, detecting with an ultraviolet detector at a wavelength of 365nm, feeding 50-200 μ L of sample each time, collecting 39.6min chromatographic peaks, and evaporating to dryness after multiple accumulation.
The invention has no limit to the granularity of the waste residue powder.
The flavonoid compound can increase the sweet feeling of cigarette smoke, relieve the stimulation of the throat after smoking and has the effects of clearing and benefiting the throat.
The structure of the flavonoid compound prepared by the above method was determined by the following method:
the compounds of the invention are pale yellow gums; HRESI-MS shows that the peak of the excimer ion is 335.0886 [ M + Na ]]+(calculated 335.0895), combined1H NMR and DEPT spectra confirm that the molecular formula is C18H16O5The unsaturation degree was 11.
The IR spectrum showed hydroxy (3428), carbonyl (1665) and aromatic rings (1618, 1459 and 1410cm-1) The resonance absorption peak of (1). The maximum absorption of the ultraviolet spectrum at 210, 262 and 365nm also indicates that aromatic ring structures possibly exist in the compound.
Process for preparing compounds1H and13c NMR spectra (see Table 1, FIG. 1 and FIG. 2) show that they contain 17 carbons and 14 hydrogens, including 1,2,3,4, 5-pentasubstituted benzene ring (C-5. about. C-10, H-8), 1, 2-disubstituted benzene ring (C-1 'to C-6', H-3 'to H-6'), 1 α -unsaturated carbonyl (C-4), 1 set of double bonds (C-2 and C-3, H-3), 1 methyl group (C- (2-C-3, H-3))d C7.91 q，d H2.49 s), two methoxy groups (d C56.4 q and 55.9 q,d H3.82 s and 3.85 s), and 1 phenolic hydroxyl group(s) ((ii)d H13.93 s) the compound was presumed to be a flavonoid based on the typical 2 benzene rings, α -unsaturated carbonyl and double bond signals, and the compound was further confirmed to be a flavonoid based on the HMBC correlation of H-3 and C-1', as well as H-6' and C-2 (see FIG. 3).
After the parent compound is identified, the remaining substituents, methyl, methoxy and phenolic hydroxyl, can be considered as substituents on the flavone.Two methoxyhydrogens (A), (B) can be observed in the HMBC spectrum of the compound (as shown in FIG. 3)d H3.82 and 3.85) with C-2' ((II)d C156.3) and C-7(d C165.9) and presumably two methoxy groups are substituted at the C-2' and C-7 positions, respectively; according to methyl hydrogen (d H2.48) with HMBC at C-5, C-6, C-7, it was confirmed that the methyl substitution was at the C-6 position; according to phenolic OH group hydrogen (d H13.93) and HMBC at C-5, C-6 and C-10, it was confirmed that the phenolic hydroxyl group was substituted at the C-5 position, respectively. In addition the proton signal on the benzene ring is typical (H-8,d H6.82 s；H-3′， d H7. 13(d) 7.6；H-4′，d H7.32 (t) 7.6；H-5′，d H6.88 (t) 7.6；H-6′，d H7.91 (d) 7.6) it was also confirmed that the flavone compounds of the present invention are trisubstituted at the 5,6, 7-position in the B ring and monosubstituted at the 2' -position in the C ring.
To this end, the structure of the compound was determined and designated as compound: 5-hydroxy-2', 7-dimethoxy-6-methyl-flavone.
Infrared, ultraviolet and mass spectral data of compounds: the UV (methanol) light is emitted from the UV,λ max(logε) 210 (4.73), 262(4.35), 365 (3.82) nm; IR (potassium bromide pellet):ν max3428、1665、1618、1459、1410、1362、1172、1038、846、785 cm-1；1h and13c NMR data (400 and 100 MHz, (C)5D5N), see Table-1; positive ion mode ESIMSm/z335 [M+Na]+(ii) a Positive ion mode HRESIMSm/z335.0886 [M+Na]+(calculation value C)18H16NaO5，335.0895)。
TABLE 1 preparation of the compounds of the invention1H NMR and13c NMR data (C)5D5N)
The third object of the present invention is achieved by:
the flavonoid compounds in the rose waste residue are used for preparing cigarette filter additives.
The present invention contemplates that glyceryl triacetate is the most commonly used plasticizer for cigarette filter formation, and that the compounds of the present invention are soluble in glyceryl triacetate, through which they can be added to the filter during cigarette filter formation.
The cigarette for adding cigarette is Hongta mountain classic, and the flavone compound is prepared into 0.5mg/mL solution by using triacetyl glycerine. Uniformly spraying the mixture on filter tow in an amount of 5-8% of the weight of the filter tow to prepare a filter stick, then making the filter stick into a cigarette by conventional cigarette rolling, performing sensory evaluation, and using the same cigarette without the compound as a reference. The evaluation and analysis result shows that: compared with the contrast, the compound of the invention is added into the cigarette filter, increases the sweet feeling of smoke, relieves the stimulation of the throat after smoking, and can obviously improve the smoking quality of the cigarette.
Compared with the prior art, the invention has the beneficial effects that:
the compound is obtained by separating waste residues after the rose essential oil is produced, and has very wide raw material sources and low cost; the compound can comprehensively utilize waste resources in production, and has important practical significance for improving the added value of rose processing.
The compound has simple structure, can be produced by artificial synthesis, is easy to realize, and provides a new additive for the tobacco industry. The compound is dissolved in the glycerol triacetate, and can be added into a filter tip through the glycerol triacetate in the forming process of the cigarette filter tip, so that no additional process is added, and the application in the cigarette is easy to realize.
Compared with the contrast, the compound is added into the cigarette filter, so that the sweet feeling of smoke is increased, the stimulation of the throat after smoking is relieved, the effects of clearing and benefiting the throat are obvious, and the effect of improving the smoking quality of the cigarette is very obvious.
Drawings
FIG. 1 nuclear magnetic resonance carbon spectrum of flavonoid compound of the present invention: (13C NMR）；
FIG. 2 shows flavonoids according to the present inventionNuclear magnetic resonance hydrogen spectrum of (A), (B), (C)1H NMR）；
FIG. 3 is a key HMBC correlation chart of the flavonoid compounds of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The materials or equipment used are not indicated by manufacturers, and all are conventional products available by purchase.
The flavonoid compounds in the rose waste residue are separated from the waste residue after the rose essential oil is produced, and are named as: 5-hydroxy-2',7-dimethoxy-6-methyl-flavone, english name: 5-hydroxy-2', 7-dimethoxy-6-methyl-flavanone with molecular formula C18H16O5The structural formula is shown as the formula (I):
The compound was a pale yellow gum, designated: the compound was named: 5-hydroxy-2',7-dimethoxy-6-methyl-flavone, english name: 5-hydroxy-2', 7-dimethoxy-6-methyl-flavanone.
The preparation method of the flavonoid compound takes waste residue after rose essential oil production as a raw material, and the flavonoid compound is prepared by the steps of extract extraction, organic solvent extraction, MCI (methanol to olefins) decoloration, silica gel column chromatography and high performance liquid chromatography separation, and specifically comprises the following steps:
A. extracting the extractum: ultrasonically extracting the waste residue powder after the rose essential oil is produced for 2-5 times by using a solvent, wherein the mass of the extraction solvent used each time is 2-6 times of that of the waste residue powder, the extraction time is 30-60 minutes each time, combining the extracting solutions, filtering, concentrating the filtrate under reduced pressure until just precipitates are separated out, standing for 20-60 minutes, filtering out the precipitates, and then concentrating the obtained filtrate under reduced pressure to obtain an extract a;
B. organic solvent extraction: adding water with the weight 1-2 times that of the extract a into the extract a, extracting for 3-5 times by using an organic solvent, combining organic solvent extraction phases, and then concentrating the combined organic solvent extraction phases under reduced pressure to obtain an extract b, wherein the volume of the organic solvent used in each time is the same as that of the water;
C. MCI decoloration: adding a 95% methanol aqueous solution with volume concentration which is 3-5 times of the weight of the extract b into the extract b, loading the extract b on an MCI (methanol-to-oil) column after the extract b is completely dissolved, eluting by using a 90-95% methanol aqueous solution, merging the eluents, and then concentrating the merged eluents under reduced pressure to obtain an extract c;
D. silica gel column chromatography: performing silica gel column chromatography on the extract c, wherein the silica gel filled in the column is 160-200 meshes, and the weight of the silica gel is 6-10 times that of the extract c; performing gradient elution by using a chloroform-acetone mixed organic solvent with a volume ratio of 1: 0-0: 1, and replacing the next gradient elution after each gradient elution is performed until no point exists on a TLC spot plate; collecting gradient eluates of each gradient, concentrating, monitoring by TLC, and mixing the same fractions;
E. high performance liquid chromatography separation: and (3) separating and purifying the part eluted by the chloroform-acetone mixed organic solvent with the volume ratio of 6:4 by adopting high performance liquid chromatography to obtain the flavonoid compound.
The solvent in the step A is an acetone aqueous solution with volume concentration of 70-100%, an ethanol aqueous solution with volume concentration of 90-100% or a methanol aqueous solution with volume concentration of 90-100%.
And the organic solvent in the step B is dichloromethane, chloroform, ethyl acetate, diethyl ether or petroleum ether.
And D, dissolving the extract c in acetone or methanol which is 1.5-3 times of the weight of the extract c before the extract c is subjected to silica gel column chromatography, mixing the sample with 80-100 meshes of silica gel which is 0.8-1.2 times of the weight of the extract c, and then loading the sample.
In the step D, in the gradient elution, the volume ratio of the chloroform to the acetone mixed organic solvent is 20:1, 9:1, 8:2, 7:3, 6:4 and 1:1 in sequence; after each gradient eluted to the point where the TLC spot plate was no longer spotted, the next gradient elution was changed.
And the high performance liquid chromatography separation and purification of the step E takes a methanol aqueous solution with the volume concentration of 40% as a mobile phase, the flow rate is 15-25 ml/min, a Zorbax PrepHT GF reversed-phase preparation column with the thickness of 21.2 multiplied by 250mm and 5 mu m as a stationary phase, the detection wavelength of an ultraviolet detector is 365nm, 50-200 mu L of sample is fed each time, a chromatographic peak of 39.6min is collected, and the chromatographic peak is evaporated to dryness after multiple accumulation.
The compound of the invention is added into a cigarette filter, and has obvious effect of improving the comfort of the cigarette suction throat; compared with the control, the cigarette can coordinate with the fragrance of the tobacco, increase the sweet feeling of the smoke, relieve the stimulation of the throat after smoking, have obvious effects of clearing and benefiting the throat and improve the smoking quality of the cigarette.
Example 1
The waste residue sample after producing the rose essential oil is from Yuxi yunnan, and the variety is Damascus rose.
A. Extracting the extractum: ultrasonically extracting the waste residue powder after the rose essential oil is produced with a solvent for 2 times, wherein the mass of the extraction solvent used each time is 2 times of that of the waste residue powder, the extraction time is 30 minutes each time, combining the extracting solutions, filtering, concentrating the filtrate under reduced pressure until just precipitate is separated out, standing for 20 minutes, filtering out the precipitate, and then concentrating the obtained filtrate under reduced pressure to obtain an extract a;
B. organic solvent extraction: adding water with the weight 1 time that of the extract a into the extract a, extracting for 3 times by using an organic solvent, combining organic solvent extraction phases, and then concentrating the combined organic solvent extraction phases under reduced pressure to obtain an extract b, wherein the volume of the organic solvent used in each time is the same as that of the water;
C. MCI decoloration: adding a 95% methanol aqueous solution with volume concentration which is 3 times of the weight of the extract b into the extract b, loading the extract b on an MCI column after the extract b is completely dissolved, eluting by using a 90% methanol aqueous solution, merging the eluents, and then concentrating the merged eluents under reduced pressure to obtain an extract c;
D. silica gel column chromatography: dissolving the extract c by using acetone or methanol with the weight 1.5 times that of the extract c, then mixing the sample by using 80-mesh silica gel with the weight 0.8 times that of the extract c, then carrying out column chromatography on the sample, wherein the silica gel filled in the column is 160 meshes, and the weight of the used silica gel is 6 times that of the extract c; performing gradient elution by using a mixed organic solvent of chloroform and acetone in a volume ratio of 20:1, 9:1, 8:2, 7:3, 6:4 and 1:1, and replacing the next gradient elution after each gradient elution is performed until no point exists on a TLC point plate; collecting gradient eluates of each gradient, concentrating, monitoring by TLC, and mixing the same fractions;
E. high performance liquid chromatography separation: separating and purifying a part eluted by a chloroform-acetone mixed organic solvent with a volume ratio of 6:4 by using a high performance liquid chromatography, wherein the specific method for separating and purifying the high performance liquid chromatography is as follows: taking 40% methanol aqueous solution as mobile phase, flowing at 15ml/min, taking 21.2 × 250mm, 5 μm Zorbax PrepHT GF reversed phase preparation column as stationary phase, detecting wavelength at 365nm by ultraviolet detector, injecting 50 μ L each time, collecting 39.6min chromatographic peak, accumulating for multiple times, and evaporating to dryness to obtain the flavonoid compound.
Wherein, the solvent in the step A is acetone aqueous solution with the volume concentration of 70 percent. And the organic solvent in the step B is chloroform.
Example 2
The waste residue sample after producing the rose essential oil is from Yuxi yunnan, and the variety is Damascus rose.
A. Extracting the extractum: ultrasonically extracting the waste residue powder after the rose essential oil is produced with a solvent for 5 times, wherein the mass of the extraction solvent used each time is 6 times of that of the waste residue powder, the extraction time is 60 minutes each time, combining the extracting solutions, filtering, concentrating the filtrate under reduced pressure until just precipitate is separated out, standing for 60 minutes, filtering out the precipitate, and then concentrating the obtained filtrate under reduced pressure to obtain an extract a;
B. organic solvent extraction: adding water with the weight 2 times that of the extract a into the extract a, extracting for 5 times by using an organic solvent, combining organic solvent extraction phases, and then concentrating the combined organic solvent extraction phases under reduced pressure to obtain an extract b, wherein the volume of the organic solvent used in each time is the same as that of the water;
C. MCI decoloration: adding a 95% methanol aqueous solution with volume concentration which is 5 times of the weight of the extract b into the extract b, loading the extract b on an MCI column after the extract b is completely dissolved, eluting by using the 95% methanol aqueous solution, merging the eluents, and then concentrating the merged eluents under reduced pressure to obtain an extract c;
D. silica gel column chromatography: dissolving the extract c by using acetone or methanol with the weight 3 times that of the extract c, then mixing the sample by using 100-mesh silica gel with the weight 1.2 times that of the extract c, then carrying out column chromatography on the sample, wherein the silica gel filled in the column is 200 meshes, and the weight of the silica gel is 10 times that of the extract c; performing gradient elution by using a mixed organic solvent of chloroform and acetone in a volume ratio of 20:1, 9:1, 8:2, 7:3, 6:4 and 1:1, and replacing the next gradient elution after each gradient elution is performed until no point exists on a TLC point plate; collecting gradient eluates of each gradient, concentrating, monitoring by TLC, and mixing the same fractions;
E. high performance liquid chromatography separation: separating and purifying a part eluted by a chloroform-acetone mixed organic solvent with a volume ratio of 6:4 by using a high performance liquid chromatography, wherein the specific method for separating and purifying the high performance liquid chromatography is as follows: taking 40% methanol aqueous solution as mobile phase, flowing at 25ml/min, taking 21.2 × 250mm, 5 μm Zorbax PrepHT GF reversed phase preparation column as stationary phase, detecting wavelength at 365nm by ultraviolet detector, feeding 200 μ L each time, collecting 39.6min chromatographic peak, accumulating for multiple times, and evaporating to dryness to obtain the flavonoid compound.
Wherein, the solvent in the step A is acetone. The organic solvent in the step B is dichloromethane.
Example 3
The waste residue sample after producing the rose essential oil is from Yuxi yunnan, and the variety is Damascus rose.
A. Extracting the extractum: ultrasonically extracting the waste residue powder after the rose essential oil is produced with a solvent for 3 times, wherein the mass of the extraction solvent used each time is 3 times of that of the waste residue powder, the extraction time is 40 minutes each time, combining the extracting solutions, filtering, concentrating the filtrate under reduced pressure until just precipitate is separated out, standing for 40 minutes, filtering out the precipitate, and then concentrating the obtained filtrate under reduced pressure to obtain an extract a;
B. organic solvent extraction: adding water with the weight 1.5 times of the weight of the extract a into the extract a, extracting for 4 times by using an organic solvent, combining organic solvent extraction phases, and then concentrating the combined organic solvent extraction phases under reduced pressure to obtain an extract b, wherein the volume of the organic solvent used in each time is the same as that of the water;
C. MCI decoloration: adding a 95% methanol aqueous solution with volume concentration 4 times of the weight of the extract b into the extract b, loading the extract b on an MCI column after the extract b is completely dissolved, eluting by using a 93% methanol aqueous solution, merging the eluents, and then concentrating the merged eluents under reduced pressure to obtain an extract c;
D. silica gel column chromatography: dissolving the extract c with acetone or methanol 2 times the weight of the extract c, mixing with 90-mesh silica gel 1 times the weight of the extract c, loading the sample, performing column chromatography, wherein the silica gel filled in the column is 180 meshes, and the weight of the silica gel is 8 times the weight of the extract c; performing gradient elution by using a mixed organic solvent of chloroform and acetone in a volume ratio of 20:1, 9:1, 8:2, 7:3, 6:4 and 1:1, and replacing the next gradient elution after each gradient elution is performed until no point exists on a TLC point plate; collecting gradient eluates of each gradient, concentrating, monitoring by TLC, and mixing the same fractions;
E. high performance liquid chromatography separation: separating and purifying a part eluted by a chloroform-acetone mixed organic solvent with a volume ratio of 6:4 by using a high performance liquid chromatography, wherein the specific method for separating and purifying the high performance liquid chromatography is as follows: taking 40% methanol aqueous solution as mobile phase, flowing at 20ml/min, taking 21.2 × 250mm, 5 μm Zorbax PrepHT GF reversed phase preparation column as stationary phase, detecting wavelength at 365nm by ultraviolet detector, feeding 100 μ L each time, collecting 39.6min chromatographic peak, accumulating for multiple times, and evaporating to dryness to obtain the flavonoid compound.
Wherein, the solvent in the step A is ethanol. And the organic solvent in the step B is ethyl acetate.
In the embodiment, 4.4kg of waste residue powder is adopted to obtain 120g of extract a, 80g of extract b, 62g of extract c, and 18g of part eluted by chloroform-acetone mixed organic solvent with the volume ratio of 6: 4.
Example 4
The waste residue sample after producing the rose essential oil comes from Xinjiang Hotan and the variety is Damascus rose.
A. Extracting the extractum: ultrasonically extracting the waste residue powder after the rose essential oil is produced with a solvent for 4 times, wherein the mass of the extraction solvent used each time is 4 times of that of the waste residue powder, the extraction time is 50 minutes each time, combining the extracting solutions, filtering, concentrating the filtrate under reduced pressure until just precipitate is separated out, standing for 40 minutes, filtering out the precipitate, and then concentrating the obtained filtrate under reduced pressure into an extract a;
B. organic solvent extraction: adding water with the weight 1.2 times of the weight of the extract a into the extract a, extracting for 4 times by using an organic solvent, combining organic solvent extraction phases, and then concentrating the combined organic solvent extraction phases under reduced pressure to obtain an extract b, wherein the volume of the organic solvent used in each time is the same as that of the water;
C. MCI decoloration: adding 95% methanol aqueous solution 4.5 times the weight of the extract b, loading the extract b on MCI column after the extract b is completely dissolved, eluting with 92% methanol aqueous solution, mixing eluates, and concentrating the mixed eluates under reduced pressure to obtain extract c;
D. silica gel column chromatography: dissolving the extract c by acetone or methanol with the weight 2.5 times that of the extract c, mixing the sample by 80-mesh silica gel with the weight 0.9 time that of the extract c, loading the sample to perform column chromatography, wherein the silica gel filled in the column is 160 meshes, and the weight of the silica gel is 8 times that of the extract c; performing gradient elution by using a mixed organic solvent of chloroform and acetone in a volume ratio of 20:1, 9:1, 8:2, 7:3, 6:4 and 1:1, and replacing the next gradient elution after each gradient elution is performed until no point exists on a TLC point plate; collecting gradient eluates of each gradient, concentrating, monitoring by TLC, and mixing the same fractions;
E. high performance liquid chromatography separation: separating and purifying a part eluted by a chloroform-acetone mixed organic solvent with a volume ratio of 6:4 by using a high performance liquid chromatography, wherein the specific method for separating and purifying the high performance liquid chromatography is as follows: taking 40% methanol aqueous solution as mobile phase, flowing at 23ml/min, taking 21.2 × 250mm, 5 μm Zorbax PrepHT GF reversed phase preparation column as stationary phase, detecting wavelength at 365nm by ultraviolet detector, injecting 80 μ L each time, collecting 39.6min chromatographic peak, accumulating for multiple times, and evaporating to dryness to obtain the flavonoid compound.
Wherein, the solvent in the step A is methanol. And the organic solvent in the step B is diethyl ether.
In the embodiment, 10kg of waste residue powder is adopted to obtain 350g of extract a, 210g of extract b, 150g of extract c and 55g of part eluted by chloroform-acetone mixed organic solvent with the volume ratio of 6: 4.
Example 5
The waste residue sample after producing the rose essential oil comes from Xinjiang Hotan and the variety is Damascus rose.
A. Extracting the extractum: ultrasonically extracting the waste residue powder after the rose essential oil is produced with a solvent for 4 times, wherein the mass of the extraction solvent used each time is 5 times of that of the waste residue powder, the extraction time is 35 minutes each time, combining the extracting solutions, filtering, concentrating the filtrate under reduced pressure until just precipitate is separated out, standing for 55 minutes, filtering out the precipitate, and then concentrating the obtained filtrate under reduced pressure to obtain an extract a;
B. organic solvent extraction: adding water with the weight 1.6 times of the weight of the extract a into the extract a, extracting for 4 times by using an organic solvent, combining organic solvent extraction phases, and then concentrating the combined organic solvent extraction phases under reduced pressure to obtain an extract b, wherein the volume of the organic solvent used in each time is the same as that of the water;
C. MCI decoloration: adding 95% methanol aqueous solution 4.5 times the weight of the extract b, loading the extract b on MCI column after the extract b is completely dissolved, eluting with 94% methanol aqueous solution, mixing eluates, and concentrating the mixed eluates under reduced pressure to obtain extract c;
D. silica gel column chromatography: dissolving the extract c by acetone or methanol with the weight 2.4 times that of the extract c, mixing the sample by 100-mesh silica gel with the weight 1 times that of the extract c, loading the sample to perform column chromatography, wherein the silica gel filled in the column is 200 meshes, and the weight of the silica gel is 7 times that of the extract c; performing gradient elution by using a mixed organic solvent of chloroform and acetone in a volume ratio of 20:1, 9:1, 8:2, 7:3, 6:4 and 1:1, and replacing the next gradient elution after each gradient elution is performed until no point exists on a TLC point plate; collecting gradient eluates of each gradient, concentrating, monitoring by TLC, and mixing the same fractions;
E. high performance liquid chromatography separation: separating and purifying a part eluted by a chloroform-acetone mixed organic solvent with a volume ratio of 6:4 by using a high performance liquid chromatography, wherein the specific method for separating and purifying the high performance liquid chromatography is as follows: taking 40% methanol aqueous solution as mobile phase, flowing at 18ml/min, taking 21.2 × 250mm, 5 μm Zorbax PrepHT GF reversed phase preparation column as stationary phase, detecting wavelength at 365nm by ultraviolet detector, injecting 120 μ L each time, collecting 39.6min chromatographic peak, accumulating for multiple times, and evaporating to dryness to obtain the flavonoid compound.
Wherein, the solvent in the step A is a methanol water solution with the volume concentration of 95 percent. And the organic solvent in the step B is petroleum ether.
Example 6
The structure of the flavonoid prepared by the method of example 1 was determined by the following method:
the compounds of the invention are pale yellow gums; HRESI-MS shows that the peak of the excimer ion is 335.0886 [ M + Na ]]+(calculated 335.0895), combined1H NMR and DEPT spectra confirm that the molecular formula is C18H16O5The unsaturation degree was 11.
The IR spectrum showed hydroxy (3428), carbonyl (1665) and aromatic rings (1618, 1459 and 1410cm-1) The resonance absorption peak of (1). The maximum absorption of the ultraviolet spectrum at 210, 262 and 365nm also indicates that aromatic ring structures possibly exist in the compound.
Process for preparing compounds1H and13c NMR spectra (see Table 1, FIG. 1 and FIG. 2) show that they contain 17 carbons and 14 hydrogens, including 1,2,3,4, 5-pentasubstituted benzene ring (C-5. about. C-10, H-8), 1, 2-disubstituted benzene ring (C-1 'to C-6', H-3 'to H-6'), 1 α -unsaturated carbonyl (C-4), 1 set of double bonds (C-2 and C-3, H-3), 1 methyl group (C- (2-C-3, H-3))d C7.91 q，d H2.49 s), two methoxy groups (d C56.4 q and 55.9 q,d H3.82 s and 3.85 s), and 1 phenolic hydroxyl group(s) ((ii)d H13.93 s) the compound was presumed to be a flavonoid based on the typical 2 benzene rings, α -unsaturated carbonyl and double bond signals, and the compound was further confirmed to be a flavonoid based on the HMBC correlation of H-3 and C-1', as well as H-6' and C-2 (see FIG. 3).
After the parent compound is identified, the remaining substituents, methyl, methoxy and phenolic hydroxyl, can be considered as substituents on the flavone. Two methoxyhydrogens were observed in the HMBC spectra of the compounds (see FIG. 3)(d H3.82 and 3.85) with C-2' ((II)d C156.3) and C-7(d C165.9) and presumably two methoxy groups are substituted at the C-2' and C-7 positions, respectively; according to methyl hydrogen (d H2.48) with HMBC at C-5, C-6, C-7, it was confirmed that the methyl substitution was at the C-6 position; according to phenolic OH group hydrogen (d H13.93) and HMBC at C-5, C-6 and C-10, it was confirmed that the phenolic hydroxyl group was substituted at the C-5 position, respectively. In addition the proton signal on the benzene ring is typical (H-8,d H6.82 s；H-3′， d H7. 13(d) 7.6；H-4′，d H7.32 (t) 7.6；H-5′，d H6.88 (t) 7.6；H-6′，d H7.91 (d) 7.6) it was also confirmed that the flavone compounds of the present invention are trisubstituted at the 5,6, 7-position in the B ring and monosubstituted at the 2' -position in the C ring.
To this end, the structure of the compound was determined and designated as compound: 5-hydroxy-2', 7-dimethoxy-6-methyl-flavone.
Example 7
The compounds prepared in examples 2-5 were taken as pale yellow gums. The measurement method was the same as in example 6, and it was confirmed that the compound prepared in examples 2 to 5 was 5-hydroxy-2',7-dimethoxy-6-methyl-flavone as the flavonoid compound.
Example 8
The flavone compound prepared in any one of the embodiments 1 to 5 is used for carrying out the addition effect test of the cigarette filter, and the test conditions are as follows:
the cigarette for adding cigarette is Hongta mountain classic, and the flavone compound is prepared into 0.1 mg/mL solution by using triacetyl glycerine. Uniformly spraying the compound on the filter tow according to 8 percent of the weight of the filter tow to prepare a filter stick, then preparing the filter stick into a cigarette through conventional cigarette rolling, carrying out sensory evaluation, and taking the same cigarette without the compound as a reference. The evaluation and analysis result shows that: can coordinate with the fragrance of the tobacco, increase the sweet feeling of the smoke, relieve the stimulation of the throat after smoking, have the obvious effects of clearing and benefiting the throat and improve the smoking quality of the cigarette.
Example 9
The flavonoid compound prepared in any one of the embodiments 1 to 5 is used for carrying out the addition effect test of the cigarette filter:
the cigarette for addition is a cigarette 'Ziyun' of Hongyun river group, and the flavonoid compound is prepared into a solution of 0.5mg/mL by using triacetyl glycerine. Uniformly spraying the mixture on filter tow according to 5% of the weight of the filter tow to prepare a filter stick, then preparing the filter stick into a cigarette through conventional cigarette rolling, carrying out sensory evaluation, and taking the same cigarette without the compound as a reference. The evaluation and analysis result shows that: the compound can coordinate with the fragrance of the tobacco, increase the sweet feeling of the smoke, relieve the stimulation of the throat after smoking, have the obvious effects of clearing and benefiting the throat and improve the smoking quality of the cigarette.
The method of application of the compound of the present invention is not limited to this, and the compound may be added to an inner liner paper or the like.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A method for preparing flavonoid compounds in rose waste residue is characterized in that,
the flavonoid compound is named as: 5-hydroxy-2',7-dimethoxy-6-methyl-flavone, english name: 5-hydroxy-2', 7-dimethoxy-6-methyl-flavanone with molecular formula C18H16O5The structural formula is shown as the formula (I):
the preparation method takes waste residue after the production of the rose essential oil as a raw material, and comprises the steps of extract extraction, organic solvent extraction, MCI decoloration, silica gel column chromatography and high performance liquid chromatography separation, and specifically comprises the following steps:
A. extracting the extractum: ultrasonically extracting the waste residue powder after the rose essential oil is produced for 2-5 times by using a solvent, wherein the mass of the extraction solvent used each time is 2-6 times of that of the waste residue powder, the extraction time is 30-60 minutes each time, combining the extracting solutions, filtering, concentrating the filtrate under reduced pressure until just precipitates are separated out, standing for 20-60 minutes, filtering out the precipitates, and then concentrating the obtained filtrate under reduced pressure to obtain an extract a;
B. organic solvent extraction: adding water with the weight 1-2 times that of the extract a into the extract a, extracting for 3-5 times by using an organic solvent, combining organic solvent extraction phases, and then concentrating the combined organic solvent extraction phases under reduced pressure to obtain an extract b, wherein the volume of the organic solvent used in each time is the same as that of the water;
C. MCI decoloration: adding a 95% methanol aqueous solution with volume concentration which is 3-5 times of the weight of the extract b into the extract b, loading the extract b on an MCI (methanol-to-oil) column after the extract b is completely dissolved, eluting by using a 90-95% methanol aqueous solution, merging the eluents, and then concentrating the merged eluents under reduced pressure to obtain an extract c;
D. silica gel column chromatography: performing silica gel column chromatography on the extract c, wherein the silica gel filled in the column is 160-200 meshes, and the weight of the silica gel is 6-10 times that of the extract c; performing gradient elution by using a chloroform-acetone mixed organic solvent with a volume ratio of 1: 0-0: 1, and replacing the next gradient elution after each gradient elution is performed until no point exists on a TLC spot plate; collecting gradient eluates of each gradient, concentrating, monitoring by TLC, and mixing the same fractions;
E. high performance liquid chromatography separation: separating and purifying the part eluted by chloroform-acetone mixed organic solvent with volume ratio of 6:4 by high performance liquid chromatography to obtain the flavonoid compound;
in the step D, in the gradient elution, the volume ratio of the chloroform to the acetone mixed organic solvent is 20:1, 9:1, 8:2, 7:3, 6:4 and 1:1 in sequence; after each gradient eluted to the point where the TLC spot plate was no longer spotted, the next gradient elution was changed.
2. The method for preparing flavonoids compounds in rose residues according to claim 1, wherein the solvent in the step a is an acetone aqueous solution with a volume concentration of 70-100%, an ethanol aqueous solution with a volume concentration of 90-100%, or a methanol aqueous solution with a volume concentration of 90-100%.
3. The method for preparing flavonoids compounds in rose dregs according to claim 1, wherein the organic solvent in step B is dichloromethane, chloroform, ethyl acetate, diethyl ether or petroleum ether.
4. The method for preparing flavonoids compounds in rose residues according to claim 1, wherein in the step D, the extract c is dissolved by acetone or methanol which is 1.5-3 times of the weight of the extract c before being subjected to silica gel column chromatography, and then is mixed by 80-100 meshes of silica gel which is 0.8-1.2 times of the weight of the extract c, and then is loaded.
5. The method for producing flavonoids in rose residues according to claim 1, wherein the separation and purification by high performance liquid chromatography in step E is performed at a flow rate of 15 to 25ml/min and a flow rate of 21.2 '250 mm, 5' with an aqueous methanol solution having a volume concentration of 40% as a mobile phasemAnd (3) taking a Zorbax PrepHT GF reversed-phase preparation column of m as a stationary phase, detecting the wavelength of 365nm by using an ultraviolet detector, feeding 50-200 mL of sample each time, collecting a chromatographic peak for 39.6min, accumulating for multiple times, and evaporating to dryness.
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