Pyranolide compound and preparation method and application thereof
阅读说明：本技术 一种吡喃内酯类化合物及其制备方法和用途 (Pyranolide compound and preparation method and application thereof ) 是由 刘欣 孔维松 杨光宇 米其利 高茜 李晶 魏玉玲 陈建华 张承明 李雪梅 胡秋芬 于 2020-05-09 设计创作，主要内容包括：本发明属于植物化学技术领域,特别涉及一种吡喃内酯类化合物及其制备方法和用途。所述化合物分子式为C<Sub>17</Sub>H<Sub>20</Sub>O<Sub>4</Sub>,且具有下述结构式：<Image he="260" wi="700" file="DDA0002484690710000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>。本发明还公开了上述吡喃内酯类化合物的制备方法和用途。本发明以烟草茎皮为原料,首次提取出一种新的吡喃内酯类化合物,该化合物具有显著的抗菌活性,对大肠杆菌、金黄色葡萄球菌等的抑菌率全部达到94％以上。该化合物应用于卷烟接装纸,能够对卷烟接装纸被污染的微生物起到抑制作用。卷烟接装纸直接和口腔接触,该化合物在卷烟接装纸中的使用可避免在卷烟在吸食、传递过程中被微生物污染,有效提高了卷烟的卫生和安全性。(The invention belongs to the technical field of phytochemistry, and particularly relates to a pyranlactone compound as well as a preparation method and application thereof. The molecular formula of the compound is C 17 H 20 O 4 And has the following structural formula: . The invention also discloses a preparation method and application of the pyranolide compound. The invention takes the tobacco stem bark as the raw material, extracts a new pyranolide compound for the first time, and the compound has obvious effectThe antibacterial activity, the bacteriostasis rate to colibacillus, staphylococcus aureus and the like can reach more than 94 percent. The compound is applied to cigarette tipping paper, and can inhibit microorganisms polluting the cigarette tipping paper. The cigarette tipping paper is directly contacted with the oral cavity, and the compound can avoid the microbial contamination in the smoking and transferring processes of the cigarette when being used in the cigarette tipping paper, thereby effectively improving the sanitation and safety of the cigarette.)
1. A pyranyl lactone compound is characterized in thatThe molecular formula of the compound is C17H20O4And has the following structural formula:
。
2. a method of preparing the pyranolactone compound of claim 1, comprising the steps of:
(1) extracting the extractum: soaking tobacco stem bark serving as a raw material and an organic solvent serving as an extraction solvent for 24-72h, extracting for 3-5 times, combining the extracting solutions, filtering and concentrating into an extract; wherein the weight ratio of the extraction solvent to the tobacco stem bark is 2-4: 1;
(2) silica gel column chromatography: performing silica gel column chromatography on the extract obtained in the step (1) by using a 160-300-mesh silica gel dry method in an amount which is 2-4 times the weight of the extract, performing gradient elution by using a chloroform-acetone solution, collecting eluent of each part, and concentrating the eluent;
wherein the volume ratio of the chloroform-acetone solution is 1:0, 20:1, 9:1, 8:2, 7:3, 6:4, 1:1 and 1: 2;
(3) high-pressure liquid chromatography separation and purification: further separating and purifying 8:2 part of the eluent in the step (2) by high pressure liquid chromatography to obtain the pyranolide compound;
wherein the high pressure liquid chromatography is used for separating and purifying C with the thickness of 21.2mm × 250mm and 5 μm18And (3) carrying out chromatographic column chromatography, wherein the flow rate is 20m L/min, the mobile phase is 62% methanol water solution, the detection wavelength of an ultraviolet detector is 332nm, the sample injection is 0.5m L every time, the chromatographic peak of 34.8min is collected, and the chromatographic peak is evaporated to dryness after multiple accumulation.
3. The method according to claim 2, wherein in the step (3), the compound separated and purified by HPLC is further dissolved in methanol, and then separated and purified by gel column chromatography using methanol as a mobile phase.
4. The preparation method according to claim 2, wherein in the step (2), the extract is dissolved in 1.5-3 times by weight of methanol, ethanol or acetone before being subjected to silica gel column chromatography and then mixed with 0.8-1.2 times by weight of 80-100 mesh silica gel.
5. The method according to claim 2, wherein the extraction solvent is methanol or ethanol having a concentration of 80 to 100 wt% or acetone having a concentration of 60 to 90 wt% in step (1).
6. Use of a pyranolide compound as claimed in claim 1 in cigarette tipping paper, wherein the pyranolide compound inhibits the growth of harmful microorganisms in the tipping paper and imparts a pleasant beany note to the tipping paper.
Technical Field
The invention belongs to the technical field of phytochemistry, and particularly relates to a pyranlactone compound as well as a preparation method and application thereof.
Background
Tobacco is the most complex plant in the world in terms of chemical composition, and secondary metabolites are very abundant, and as reported by Dube and Green et al in 1982, the chemical compositions identified in tobacco are more than 2549, and by 2008, the total number of compounds found in tobacco, tobacco substitutes, and cigarette smoke is about 8700, as reported by Rodgman and perfetti. At present, more than 3000 monomer chemical substances are identified from tobacco, and many ingredients are not identified yet. Besides being mainly used for cigarette smoking, the tobacco can also extract a plurality of chemical components with useful values, and guide compounds with development and utilization values are found from the chemical components.
Pyranolactones are found in many natural plants and possess a variety of biological activities. According to the reports of documents, the compounds have the pharmacological effects of resisting tumors, oxidation, fungi and bacteria, resisting platelet aggregation, and the like. Because the pyranolide compound has the broad-spectrum pharmacological activity, researchers at home and abroad carry out deep research on the compound, and besides searching the compound from natural products, the compound with better pharmacological activity is obtained by structural modification. In order to research the structure-activity relationship of the compounds, more furan compounds can be further researched and developed, and effective lead compounds and active groups can be searched.
It is expected to find a new pyranlactone compound with various biological activities and efficacies from natural products.
Disclosure of Invention
The present invention has been made to solve the above problems.
The invention separates a new pyranolide compound from stem bark of Yunnan flue-cured tobacco, the compound has not been reported to related reports so far, and the compound has remarkable antibacterial activity and comfortable bean fragrance. The compound is applied to the cigarette tipping paper, and can effectively inhibit the propagation of harmful microorganisms in the tipping paper; and can endow the tipping paper with comfortable bean fragrance.
The invention aims to provide a novel pyranolide compound.
Another object of the present invention is to provide a method for preparing the pyranlactones.
The invention also aims to provide application of the pyranlactone compound in antibacterial tipping paper.
All percentages used in the present invention are mass percentages unless otherwise indicated.
The invention provides a pyranolide compound with a molecular formula of C in a first aspect17H20O4And has the following structural formula:
。
the invention separates a new pyranolide compound from tobacco, and the compound is named as: 6- (hydroxyethyl) -7-methoxy-3- (isopentenyl) -2H-chromen-2-one, English name: 6- (hydroxyethyl) -7-methoxy-3- (phenyl) -2H-chromen-2-one.
The pyranolide compound is yellow jelly and has a pleasant bean fragrance.
In a second aspect, the present invention provides a method for preparing a pyranolactone compound as described in the first aspect, comprising the steps of:
(1) extracting the extractum: soaking tobacco stem bark serving as a raw material in an organic solvent serving as an extraction solvent for 24-72h, extracting for 3-5 times, combining the extracting solutions, filtering and concentrating into an extract;
wherein the weight ratio of the extraction solvent to the tobacco stem bark is 2-4: 1;
(2) silica gel column chromatography: performing silica gel column chromatography on the extract obtained in the step (1) by using a 160-300-mesh silica gel dry method in an amount which is 2-4 times the weight of the extract, performing gradient elution by using a chloroform-acetone solution, collecting eluent of each part, and concentrating the eluent;
wherein the volume ratio of the chloroform-acetone solution is 1:0, 20:1, 9:1, 8:2, 7:3, 6:4, 1:1 and 1: 2;
(3) high-pressure liquid chromatography separation and purification: further separating and purifying 8:2 part of the eluent in the step (2) by high pressure liquid chromatography to obtain the pyranolide compound;
wherein the high pressure liquid chromatography is used for separating and purifying C with the thickness of 21.2mm × 250mm and 5 μm18The chromatographic column has a flow rate of 20m L/min, a mobile phase of 62% methanol water solution, and ultravioletThe wavelength detected by the detector is 332nm, 0.5m L is injected each time, 34.8min chromatographic peaks are collected, and the chromatographic peaks are evaporated to dryness after multiple accumulation.
Preferably, in step (3), the compound separated and purified by HPLC is again dissolved in methanol, and then separated by gel column chromatography using methanol as a mobile phase for further separation and purification.
Preferably, in the step (2), before the extract is subjected to silica gel column chromatography and coarse separation, the extract is dissolved by using 1.5-3 times of methanol, ethanol or acetone by weight, and then is mixed with 0.8-1.2 times of 80-100 mesh silica gel by weight.
Preferably, in the step (1), the extraction solvent is methanol or ethanol with a concentration of 80 wt% to 100 wt%, or acetone with a concentration of 60 wt% to 90 wt%.
The tobacco stem and bark raw materials used in the invention are not limited by regions and varieties, and the invention can be realized.
In a third aspect, the present invention provides the use of a pyranlactone compound as described in the first aspect in cigarette tipping paper, the pyranlactone compound being capable of inhibiting the propagation of harmful microorganisms in the tipping paper and imparting a pleasing beany note to the tipping paper.
The technical scheme can be freely combined on the premise of no contradiction.
The invention has the following outstanding advantages:
1. the invention takes the tobacco stem bark as the raw material, extracts a new pyranolide compound for the first time, the compound has obvious antibacterial activity, and the bacteriostasis rate of the compound on escherichia coli, staphylococcus aureus and the like is all more than 94%. The compound is applied to cigarette tipping paper, and can inhibit microorganisms polluting the cigarette tipping paper. The cigarette tipping paper is directly contacted with the oral cavity, and the compound can avoid the microbial contamination in the smoking and transferring processes of the cigarette when being used in the cigarette tipping paper, thereby effectively improving the sanitation and safety of the cigarette.
2. The compound is simple in extraction method and easy to separate, the compound is prepared by a preparation method combining conventional column chromatography and high performance liquid chromatography, the preparation operation flow of the compound is simple, the purity of the obtained compound is high, and the subsequent industrial production is easy to realize.
3. The safety evaluation of the compound of the invention proves that the compound of the invention is nontoxic to animals and safe to use.
4. The applicant has also surprisingly found that the compound of the present invention also has a pleasant bean-like aroma, and can impart an elegant bean-like style to the tipping paper and improve the odor effect of the tipping paper.
5. In the existing cigarette paper with fragrance, the added essence and spice provide nutrient substances for microorganisms and can promote mass propagation of harmful microorganisms. The compound has the functions of perfuming and bacteriostasis when being used in cigarette tipping paper, so that the cigarette paper with the functions of improving the cigarette smoking quality and bacteriostasis is obtained for the first time, and the problems are solved at one stroke.
Drawings
FIG. 1 shows the nuclear magnetic resonance carbon spectrum of the pyranolide compounds of the present invention.
FIG. 2 shows the NMR spectrum of the pyranolide compounds of the present invention.
FIG. 3 is a graph of the primary HMBC (H → C) correlation of the pyranolactones of the present invention.
Detailed Description
The structure of the pyranolide compound prepared by the invention is identified by the following method:
HRESI-MS shows that the peak of the excimer ion is 311.1254[ M + Na ]]+(calculated 311.1259), combined1HNMR、13C NMR and DEPT spectra to determine its molecular formula as C17H20O4The unsaturation degree is 8.
The infrared spectrum shows hydroxyl groups (3386 cm)-1) Carbonyl group (1708 cm)-1) And aromatic rings (1620, 1558 and 1462 cm)-1) The resonance absorption peak of (1). And the maximum absorption of the ultraviolet spectrum at 220nm, 270nm and 332nm also indicates that aromatic ring structures possibly exist in the compound.
Process for preparing compounds1H and13c NMR spectra (Table 1, FIG. 1 and FIG. 2) showed that it contained 17 carbons and 20 hydrogens, including a 3,6, 7-substituted benzopyranLactone mother nucleus (C-2-C-10, H-4, H-5 and H-8) and isopentenyl (-CH)2-CH＝C(CH3)2；C-1'～C-5'，H2-1'，H-2'，H3-4' and H3-5'), 1 hydroxyethyl (C-1 ' and C-2 ', H2-1 "and H2-2 ") and 1 methoxy group(s) ((iii)C56.2，H3.86). By analyzing the HMBC correlation spectrum (figure-3), the existence of the benzopyranolide parent nucleus in the compound structure can be confirmed by the correlation of H-4 and C-2, C-3, C-5, C-9 and C-10, H-5 and C-4, C-9 and C-10, H-8 and C-6, C-9 and C-10 HMBC; the presence of isopentenyl in the structure of the compound can be determined by H2-1 'with C-2' and C-3 ', H-2' with C-1 ', C-3', C-4 'and C-5', H3-4' with C-3 ' and C-2 '; and H3-5' correlation with C-3 ' and C-2 ' HMBC was confirmed; the presence of hydroxyethyl groups in the structure of the compounds can be determined by H2-1 'and C-2', H2HMBC correlation of-2 "with C-1" was confirmed.
After the parent nucleus of the compound and the substituents (isopentenyl, hydroxyethyl and methoxy) are confirmed, the position of the substituent can be further determined according to HMBC correlation spectra. By H2-1' with C-5, C-6, C-7, H22 "HMBC with C-6, H-5 with C-1" confirmed the hydroxyethyl substitution at C-6; by H2Correlation of 1 ' with C-2, C-3 and C-4, H-2 ' with C-3, H-4 with C-1 ' with HMBC confirmed the prenyl substitution at C-3; methoxy substituted in the C-7 position by methoxy hydrogen (C-7)H3.86) and C-7(C156.8) was confirmed. To this end, the structure of the compound was determined and the compound was named: 6- (ethoxyl) -7-methoxyl-3- (isopentenyl) -2H-chromene-2-ketone, which is also known by the common name: tobacco pyranolactone-B.
TABLE 1 preparation of the compounds of the invention1H NMR and13c NMR data (CDCl)3)
No.
δC(mult.)
δH(mult,J,Hz)
No.
δC(mult.)
δH(mult,J,Hz)
2
162.9s
1'
28.8t
3.32(d)7.2
3
126.1s
2'
121.5d
5.30(t)7.2
4
139.2d
7.42s
3'
134.2s
5
127.1d
7.07s
4'
26.4q
1.94s
6
124.2s
5'
21.5q
1.64s
7
156.8s
1”
31.0t
2.62(t)7.0
8
102.5d
6.78s
2”
62.9t
3.61(t)7.0
9
152.6s
-OMe-7
56.2q
3.86s
10
114.7s
Infrared, ultraviolet and mass spectral data of compounds: violet spectrum (methanol), lambdamax(log)220(4.22), 270(3.89), 332(3.90) nm; infrared spectroscopy (potassium bromide pellet): v ismax3386、2962、2273、1708、1620、1558、1462、1257、1158、1044、854cm-1；1H and13c NMR data (500 and 125MHz in CDCl as solvent)3) See Table-1; positive ion mode ESIMS M/z 311[ M + Na ]]+(ii) a Positive ion mode HRESIMS M/z 311.1254[ M + Na ]]+(calculated 311.1259, C17H20NaO4)。
The invention is further described in detail below with reference to the drawings and examples, but the invention is not limited in any way, and any changes or modifications made based on the teachings of the invention fall within the scope of the invention.
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