CN115073272B - Juniperidine sesquiterpene compound, preparation method and application thereof - Google Patents

Juniperidine sesquiterpene compound, preparation method and application thereof Download PDF

Info

Publication number
CN115073272B
CN115073272B CN202210798542.2A CN202210798542A CN115073272B CN 115073272 B CN115073272 B CN 115073272B CN 202210798542 A CN202210798542 A CN 202210798542A CN 115073272 B CN115073272 B CN 115073272B
Authority
CN
China
Prior art keywords
extract
extracting
organic solvent
silica gel
juniperidine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210798542.2A
Other languages
Chinese (zh)
Other versions
CN115073272A (en
Inventor
尚善斋
田永峰
蔡洁云
汪伟光
雷萍
李志强
韩敬美
洪鎏
张霞
赵伟
王汝�
吕茜
秦世春
朱东来
秦云华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Tobacco Yunnan Industrial Co Ltd
Original Assignee
China Tobacco Yunnan Industrial Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Tobacco Yunnan Industrial Co Ltd filed Critical China Tobacco Yunnan Industrial Co Ltd
Priority to CN202210798542.2A priority Critical patent/CN115073272B/en
Publication of CN115073272A publication Critical patent/CN115073272A/en
Application granted granted Critical
Publication of CN115073272B publication Critical patent/CN115073272B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/02—Manufacture of tobacco smoke filters
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/14—Use of materials for tobacco smoke filters of organic materials as additive
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/36—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/38—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses an aromatic cyclized juniperidine compound with a new structure, which has the following structure:
Figure DDA0003736599790000011
the name is: 4-isopropyl-7-methoxy-6-methyl-1-hydroxymethylnaphthalene; its molecular formula is C 16 H 20 O 2 . The invention also discloses a preparation method of the sesquiterpenoids and application of the sesquiterpenoids in improving smoking quality of heated cigarettes.

Description

Juniperidine sesquiterpene compound, preparation method and application thereof
Technical Field
The invention belongs to the technical field of tobacco chemistry, and particularly relates to a juniperidine compound extracted from Yunnan tobacco for the first time, a preparation method thereof and application thereof in improving sensory quality of heated cigarettes.
Background
Tobacco is one of the most complex plants in the world, the variety of secondary metabolites in tobacco is very rich, and after decades of research, the single compounds separated and identified from tobacco are as much as 3000, and many components in tobacco are not identified yet, so that the research space of tobacco chemistry is still very large. While smoking is a health hazard, smoking is still attractive to thousands of consumers. Besides the addictive nature of nicotine, tobacco has rich flavor substances, and the pleasant feeling given to consumers plays an important role.
Sesquiterpene compounds belong to one of the terpenoid family molecules, and the structure contains 15 carbon atoms and three isoprene units, and the sesquiterpene is the largest one of the terpenoid from the number point of view or the type of structural framework. Sesquiterpenoids are widely distributed, are often present in volatile oil in the form of alcohols, ketones, lactones and the like in plants, are main components of high-boiling-point parts in the volatile oil, have strong fragrance and biological activity, and are important raw materials in the industries of medicines, foods and cosmetics. In order to fully utilize the excavation of tobacco resources and further search for new active natural products, the chemical components of Yunnan tobacco are researched and separated to obtain an aromatic cyclized juniperidine type sesquiterpene with improved smoking quality of heated cigarettes, and related reports of the compound are not yet seen. The juniperidine sesquiterpene compound disclosed by the invention is added into a heating cigarette filter tip, so that a better aroma enhancement effect is achieved; compared with the control, the cigarette can effectively improve the smoking softness of the heated cigarette and enhance the sense of fluid production.
Disclosure of Invention
A first object of the present invention is to provide an aromatic cyclized juniperidine sesquiterpene compound; a second object is to provide a process for producing the sesquiterpene compound; a third object is to provide the use of said sesquiterpene compounds in the perfuming of heated cigarette filters for improving the smoking quality of heated cigarettes.
The first object of the present invention is achieved by separating a juniperidine sesquiterpene compound of formula C from tobacco 16 H 20 O 2 It has the following structure:
Figure BDA0003736599770000021
the name is: 4-isopropyl-7 methoxy-6-methyl-1-hydroxymethyl naphthalene, the english name is:
(4-isopropyl-7-methoxy-6-methylphthalen-1-yl) methyl alcohol; the compound was a pale yellow gum.
The second object of the present invention is achieved by a process for preparing the juniperidine sesquiterpene compound, comprising the steps of: taking tobacco as a raw material, and preparing and separating the tobacco by extractum extraction, organic solvent extraction, silica gel column chromatography, high performance liquid chromatography and the like; the method comprises the following steps:
(1) Extracting extract: crushing tobacco raw materials, extracting for 1-3 times by using a mixed solution of an organic solvent and water for 12-72 hours each time, merging extracting solutions, filtering, concentrating the extracting solutions under reduced pressure, standing, filtering out precipitates, and concentrating into an extract a;
(2) Extracting with an organic solvent: adding water with the weight 1-2 times of that of the extract a, extracting for 2-5 times by using an organic solvent with the same volume as that of the water, combining organic solvent extraction phases, and concentrating under reduced pressure to obtain an extract b;
(3) Silica gel column chromatography: loading the extract b on a silica gel column for chromatography, wherein the silica gel column is 160-300 meshes, and the dosage is 3-8 times of the weight of the extract b; mixing chloroform and acetone with the volume ratio of 1:0-0:1, performing gradient elution by using an organic solvent, collecting gradient eluent, concentrating, monitoring by TLC, and merging the same parts;
(4) High performance liquid chromatography separation: eluting the eluent obtained by eluting the chloroform-acetone in the ratio of 9:1, and separating and purifying by high performance liquid chromatography; the juniperidine sesquiterpene compound is obtained.
Preferably, the organic solvent of step (1) is 70-95 v/v% acetone, 90-100 v/v% ethanol or 90-100 v/v% methanol.
Preferably, the organic solvent in the step (2) is one or more of dichloromethane, chloroform, ethyl acetate, diethyl ether or petroleum ether.
Preferably, before the extract b in the step (3) is subjected to silica gel column chromatography, acetone, ethanol, methanol or a mixture thereof with the weight ratio of 1.5-3 times is used for dissolving, and then 80-100 meshes of silica gel with the weight ratio of 0.8-1.5 times is used for mixing samples.
Preferably, the volume ratio of the chloroform to the acetone mixed organic solvent in the step (3) is 20:1,9:1,8:2,7:3,6:4 and 5:5.
Preferably, the high performance liquid chromatography separation and purification in the step (4) uses 52-55 v/v% methanol as a mobile phase, the flow rate is 20ml/min, a Zorbax PrepHT GF reversed phase preparation column with the flow rate of 21.2 x 250mm and 5 mu m is used as a stationary phase, the detection wavelength of an ultraviolet detector is 308nm, 50-200 mu L of sample injection is carried out each time, chromatographic peaks with the flow rate of 34.8min are collected, and the chromatographic peaks are evaporated after accumulation for a plurality of times.
The structure of the sesquiterpenoids prepared by the above method was determined by the following method; the juniperidine sesquiterpene compound is light yellow jelly; HRESI-MS showed an excimer ion peak of 267.1367[ M+Na ]]++ (calculated 267.1361), combined with 1 The molecular formula of the catalyst is determined to be C by H NMR and DEPT spectra 16 H 20 O 2 The unsaturation was 7. The maximum absorption of the UV spectrum at 215, 256 and 308nm also indicates the presence of aromatic ring structures in the compounds. 1H and 13C NMR spectra of the compounds (data ascribed toTable 1) shows signals containing 16 carbons and 20 hydrogens, respectively, 4 methyl signals (one of which is methoxy, 2 of which is isopropyl), tetra-substituted naphthalene ring signals and one hydroxymethyl group. Based on the above signals and unsaturation, the compounds of the present invention are presumed to be juniperidine sesquiterpenes. The speculation may be further based on HMBC and 1 H- 1 the HCOSY-related signal further determines: (1) HMBC signal: the signals associated with H-8 and C-1, C-6 and C-7,H-5 and C-9, C-10, H-2 and C-1, C-9,H-14 and C-1, C-4 determine the presence of tetra-substituted naphthalene fragments; (2) 1 H- 1 H COSY: h-11 and H 6 The correlation of-12, 13 then determines the presence of isopropyl.
Further, HMBC related signals of H-11, H-12, H-13 and C-4 can determine that isopropyl is attached to C-4, H 2 The correlation signals of-14 and C-1, C-2 and C-9 can determine that hydroxymethyl is correlated with C-1, H 3 The correlation of the signals of 15 and C-5, C-6, C-7 can determine that it is linked to C-6, and the correlation of the methoxyhydrogen signal and C-7 can further determine the linking position. To this end, the structure of the compound was confirmed, and the compound was named: 4-isopropyl-7 methoxy-6-methyl-1-hydroxymethyl naphthalene, the english name is: (4-isopropyl-7-methoxy-6-methylphthalen-1-yl) methyl alcohol.
Infrared, ultraviolet and mass spectral data for the compounds: UV (methanol), lambda max (log ε) 308 (3.62), 256 (3.43), 215 (4.06) nm, IR (Potassium bromide tablet) ν max 3405，3068，2952，1615，1563，1462，1349，1264，1235，1146，958cm -1 The method comprises the steps of carrying out a first treatment on the surface of the 1H NMR and 13C NMR data (CDCl 3, 500 and 125 MH) as shown in Table-1; ESI-MS (Positive ion mode) m/z 267[ M+Na ]]++, of the material; HR-ESI-MS (positive ion mode) m/z 267.1367[ M+Na ]]++ (calculated 267.1361, C) 16 H 20 NaO 2 )。
The compounds of Table 1 1 H NMR 13 C NMR data (CDCl) 3 )
Figure BDA0003736599770000041
The third object of the invention is the application of the juniperidine sesquiterpene compound in flavoring of heating cigarette filters, which is used for improving the smoking quality of heating cigarettes. The third object of the present invention is achieved in that, considering that triacetin is the most commonly used plasticizer for the formation of heated cigarette filters, and that the compound of the present invention is soluble in triacetin, the compound of the present invention is added to the filter by triacetin during the formation of heated cigarette filters, it is easy to achieve in terms of process, and no additional steps in the production process are added. The compounds of the invention are therefore added via glycerol triacetate.
The heated cigarette is used as a sample of A-grade heated cigarette, and the sesquiterpenes are prepared into solutions of 0.1mg/mL, 0.3mg/mL and 0.5mg/mL by using glyceryl triacetate. Uniformly spraying the mixture on the filter tow according to the weight of 3% -8% of the filter tow to prepare a filter stick, then connecting the filter stick to a conventional heating cigarette to prepare a heating cigarette, performing sensory evaluation, and taking the same heating cigarette without the compound as a control. The evaluation results show that: compared with a control sample, the heated cigarette with the compound of the invention added in the filter tip has improved fragrance richness and softness, obvious salivation promoting effect and obviously improved smoking quality.
The beneficial effects of the invention are as follows:
1. the juniperidine type sesquiterpene compound is separated from tobacco for the first time, is used as an endogenous aroma component of the tobacco, is used for improving the smoking quality of a heated cigarette, is safe to use, has good style coordination with the product, and does not cause obvious change of the style characteristics of the cigarette.
2. The juniperidine type sesquiterpene compound provided by the invention has the advantages of wide sources of raw materials for preparing the juniperidine type sesquiterpene compound, low extraction and separation preparation cost and easiness in realization of subsequent industrialization. Moreover, the compound has a relatively simple structure, is easy to realize artificial synthesis, is expected to realize quantitative production in the future through a synthesis process, and provides a novel additive for improving the quality of heated cigarettes.
3. The juniperidine sesquiterpene compound disclosed by the invention can be dissolved in glycerol triacetate for addition. Since glycerol triacetate is the most commonly used plasticizer for cigarette filter formation, it is easy to achieve in terms of process by adding glycerol triacetate to the filter without adding additional steps in the production process.
4. The juniperidine sesquiterpene compound disclosed by the invention is used for improving the smoking quality of a heating cigarette, is small in addition amount, has a good quality improvement effect by adding a small amount of the juniperidine sesquiterpene compound into a heating cigarette filter stick, can improve the smoking softness of the heating cigarette, enhances the salivation feeling of the heating cigarette, and improves the smoking quality of the cigarette.
Drawings
FIG. 1 shows the nuclear magnetic resonance carbon spectrum (13C NMR) of the sesquiterpenoids of the invention.
FIG. 2 shows the nuclear magnetic resonance hydrogen spectrum (1H NMR) of the sesquiterpenoids of the invention.
FIG. 3 key HMBC related to sesquiterpenes of the invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings, without limiting the invention in any way, and any alterations or modifications based on the teachings of the invention fall within the scope of the invention.
The juniperidine sesquiterpene compound is separated from tobacco, and has a molecular formula of C 16 H 20 O 2 The structure is as follows:
Figure BDA0003736599770000051
the name is: 4-isopropyl-7 methoxy-6-methyl-1-hydroxymethyl naphthalene, the english name is:
(4-isopropyl-7-methoxy-6-methylphthalen-1-yl) methyl alcohol; the compound was a pale yellow gum.
The method comprises the steps of taking tobacco as a raw material, extracting by using an extract, extracting by using an organic solvent, and preparing and separating by using silica gel column chromatography and high performance liquid chromatography; the method comprises the following steps:
(1) Extracting extract: crushing tobacco raw materials, extracting for 1-3 times by using a mixed solution of an organic solvent and water for 12-72 hours each time, merging extracting solutions, filtering, concentrating the extracting solutions under reduced pressure, standing, filtering out precipitates, and concentrating into an extract a;
(2) Extracting with an organic solvent: adding water with the weight 1-2 times of that of the extract a, extracting for 2-5 times by using an organic solvent with the same volume as that of the water, combining organic solvent extraction phases, and concentrating under reduced pressure to obtain an extract b;
(3) Silica gel column chromatography: loading the extract b on a silica gel column for chromatography, wherein the silica gel column is 160-300 meshes, and the dosage is 3-8 times of the weight of the extract b; mixing chloroform and acetone with the volume ratio of 1:0-0:1, performing gradient elution by using an organic solvent, collecting gradient eluent, concentrating, monitoring by TLC, and merging the same parts;
(4) High performance liquid chromatography separation: eluting the eluent obtained by eluting the chloroform-acetone in the ratio of 9:1, and separating and purifying by high performance liquid chromatography; the juniperidine sesquiterpene compound is obtained.
Preferably, the organic solvent of step (1) is 70-95 v/v% acetone, 90-100 v/v% ethanol or 90-100 v/v% methanol.
Preferably, the organic solvent in the step (2) is one or more of dichloromethane, chloroform, ethyl acetate, diethyl ether or petroleum ether.
Preferably, before the extract c in the step (3) is subjected to silica gel column chromatography, acetone, ethanol, methanol or a mixture thereof with the weight ratio of 1.5-3 times is used for dissolving, and then 80-100 meshes of silica gel with the weight ratio of 0.8-1.5 times is used for mixing samples.
Preferably, the volume ratio of the chloroform to the acetone mixed organic solvent in the step (3) is 20:1,9:1,8:2,7:3,6:4 and 5:5.
Preferably, the high performance liquid chromatography separation and purification in the step (4) uses 52-55 v/v% methanol as a mobile phase, the flow rate is 20ml/min, a Zorbax PrepHT GF reversed phase preparation column with the flow rate of 21.2 x 250mm and 5 mu m is used as a stationary phase, the detection wavelength of an ultraviolet detector is 308nm, 50-200 mu L of sample injection is carried out each time, chromatographic peaks with the flow rate of 34.8min are collected, and the chromatographic peaks are evaporated after accumulation for a plurality of times.
The tobacco raw materials used in the invention are not limited by regions and varieties, and the invention can be realized.
Example 1
Taking 12kg of dried tobacco, coarsely crushing, leaching with 70% acetone for 3 times, each time for 24 hours, and combining the extracting solutions; filtering the extract, and concentrating under reduced pressure to 1/5 of the volume; standing, filtering out precipitate, and concentrating into 310g of extract a; adding 450g of water into the extract a, extracting for 5 times by using chloroform with the same volume as the water, combining the extracted phases, and concentrating under reduced pressure to 176g of extract b; adding 150g of acetone into the extract b for dissolution, then adding 150g of 60-mesh silica gel for sample mixing, and filling a column with 600g of 200-mesh silica gel after sample mixing; gradient eluting with chloroform-acetone mixed organic solvent with volume ratio of 20:1,9:1,8:2,7:3,6:4 and 5:5 respectively, collecting gradient eluent, concentrating, monitoring by TLC, combining the same parts to obtain 6 parts A-F, wherein 29.5g of the collected sample B (9:1) is subjected to multi-accumulation and evaporation to dryness to obtain the novel compound by using 52% methanol as mobile phase, using a Zorbax PrepHT GF reversed phase preparation column with flow rate of 20ml/min and 21.2X105 mm and 5 μm as stationary phase, detecting wavelength by an ultraviolet detector of 308nm, sampling 60 mu L each time, collecting chromatographic peaks for 34.8 min.
Example 2
Taking 10kg of dried tobacco, coarsely crushing to 40 meshes, carrying out cold leaching extraction for 4 times by using 95% ethanol for 48 hours each time, and merging the extracting solutions; filtering the extract, and concentrating under reduced pressure to 1/4 of the volume; standing, filtering out precipitate, and concentrating to 430g of extract a; adding 300g of water into the extract a, extracting for 5 times by using ethyl acetate with the same volume as the water, combining the extracted phases, and concentrating under reduced pressure to obtain 190g of extract b; filling the extract b into a column by using MCI, adding 800g of 80% methanol water into the extract b for dissolution, then filling the column, eluting with 5 to 15 liters of 90% methanol water, collecting eluent, and concentrating under reduced pressure to obtain 167g of extract c; adding 180g of acetone into the extract c for dissolution, then adding 180g of 80-mesh silica gel for sample stirring, loading a column with 900g of 200-mesh silica gel, and loading the column after sample stirring; gradient eluting with chloroform-acetone mixed organic solvent with volume ratio of 20:1,9:1,8:2,7:3,6:4 and 5:5 respectively, collecting gradient eluent, concentrating, monitoring by TLC, combining the same parts to obtain 6 parts A-F, wherein 26.3g of the collected sample B (9:1) part is subjected to multi-accumulation and evaporation to dryness to obtain the novel compound by using 52% methanol as mobile phase, using a Zorbax PrepHT GF reversed phase preparation column with flow rate of 20ml/min and 21.2X105 mm and 5 μm as stationary phase, detecting wavelength by an ultraviolet detector of 308nm, sampling 100 mu L each time, collecting chromatographic peaks for 34.8 min.
Example 3
Taking the compound prepared in the example 1 as a pale yellow jelly, and having weak floral fragrance; the measuring method comprises the following steps: nuclear magnetic resonance, in combination with other spectroscopic techniques, is used to identify structures. The structure of the sesquiterpenoids prepared by the above method was determined by the following method; the compound of the invention is a pale yellow jelly; HRESI-MS showed an excimer ion peak of 267.1367[ M+Na ]]++ (calculated 267.1361), molecular formula C was determined by combining 1H NMR and DEPT spectra 16 H 20 O 2 The unsaturation was 7. Hydroxyl groups (3396 cm) are shown in the IR spectrum -1 ) Carbonyl (1658 cm) -1 ) And aromatic rings (1612, 1562, 1441 cm) -1 ) Is a resonance absorption peak of (2). The maximum absorption at 215, 256 and 308nm of the UV spectrum also indicates the presence of aromatic ring structures in the compounds. Of compounds 1 H and 13 the C NMR spectrum (data ascribed to Table 1) shows signals containing 16 carbons and 20 hydrogens, 4 methyl signals (one of which is methoxy and 2 is isopropyl), tetra-substituted naphthalene ring signals and one hydroxymethyl group, respectively. Based on the above signals and unsaturation, the compounds of the present invention are presumed to be juniperidine sesquiterpenes. The speculation may be further based on HMBC and 1 H- 1 the H COSY related signal is further determined: (1) HMBC signal: h-8 and C-1, C-6 and C-7,H-5 and C-9, C-10, H-2 and C-1, C-9,H-1 and C-1, C-4; (2) 1H-1H COSY: h-11 and H 6 -12,13。
Further, HMBC related signals of H-11, H-12, H-13 and C-4 can determine that isopropyl is attached to C-4, H 2 The correlation signals of-14 and C-1, C-2 and C-9 can determine that hydroxymethyl is correlated with C-1, H 3 The correlation of the signals of-5 and C-5, C-6, C-7 can determine that it is linked to C-6, and the correlation of the methoxyhydrogen signal and C-7 can further determine the linking position. To this end, the structure of the compound was confirmed, and the compound was named: 4-isopropyl-7 methoxy-6-methyl-1-hydroxymethyl naphthalene, the english name is: (4-isopropyl-7-methoxy-6-methylphthalen-1-yl) methyl alcohol. FIG. 3 key HMBC related to sesquiterpenes of the invention.
Example 4
The compound prepared in example 2 was taken as a pale yellow gum. The measurement was the same as in example 3, and the compound prepared in example 2 was confirmed to be the sesquiterpenoid: 4-isopropyl-7-methoxy-6-methyl-1-hydroxymethylnaphthalene.
Example 5
The juniperidine type sesquiterpene compound prepared in any of the embodiments 1-2 is adopted for a flavoring effect test of a heating cigarette filter tip, a heating cigarette is added to be a heating cigarette sample of a brand A of Yunnan medium smoke, and the sesquiterpene compound is prepared into a solution of 0.5mg/mL by using glyceryl triacetate. Uniformly spraying the mixture on the filter tow according to 5% of the weight of the filter tow to prepare a filter stick, then connecting the filter stick with a conventional heating cigarette to prepare a heating cigarette, performing sensory evaluation, and taking the same heating cigarette without the compound as a control. The evaluation results show that: compared with a control sample, the heated cigarette with the compound of the invention added in the filter tip has improved fragrance richness and softness, obvious salivation promoting effect and obviously improved smoking quality.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (7)

1. A juniperidine sesquiterpene compound characterized by the following structure:
Figure FDA0004252504350000011
the name is: 4-isopropyl-7-methoxy-6-methyl-1-hydroxymethylnaphthalene; its molecular formula is C 16 H 20 O 2 。
2. A process for the preparation of a juniperidine sesquiterpene compound according to claim 1, comprising the steps of: the method comprises the steps of taking tobacco as a raw material, extracting by using an extract, extracting by using an organic solvent, and preparing and separating by using silica gel column chromatography and high performance liquid chromatography; the method comprises the following steps:
(1) Extracting extract: crushing tobacco raw materials, extracting for 1-3 times by using a mixed solution of an organic solvent and water for 12-72 hours each time, merging extracting solutions, filtering, concentrating the extracting solutions under reduced pressure, standing, filtering out precipitates, and concentrating into an extract a;
(2) Extracting with an organic solvent: adding water with the weight 1-2 times of that of the extract a, extracting for 2-5 times by using an organic solvent with the same volume as that of the water, combining organic solvent extraction phases, and concentrating under reduced pressure to obtain an extract b;
(3) Silica gel column chromatography: loading the extract b on a silica gel column for chromatography, wherein the silica gel column is 160-300 meshes, and the dosage is 3-8 times of the weight of the extract b; mixing chloroform and acetone with volume ratio of 20:1,9:1,8:2,7:3,6:4 and 5:5, performing gradient elution, collecting gradient eluent, concentrating, monitoring by TLC, and mixing the same parts;
(4) High performance liquid chromatography separation: eluting the eluent obtained by eluting the chloroform-acetone in the ratio of 9:1, and separating and purifying by high performance liquid chromatography; the sesquiterpenoids are obtained.
3. The process according to claim 2, wherein the organic solvent in the step (1) is 70 to 95v/v% acetone, 90 to 100v/v% ethanol or 90 to 100v/v% methanol.
4. The preparation method according to claim 2, wherein the organic solvent in the step (2) is one or more of dichloromethane, chloroform, ethyl acetate, diethyl ether or petroleum ether.
5. The preparation method according to claim 2, wherein the extract b in the step (3) is dissolved in 1.5 to 3 times by weight of acetone, ethanol, methanol or a mixture thereof before passing through the silica gel column chromatography, and then is stirred with 80 to 100 mesh silica gel having an extract weight of 0.8 to 1.5 times.
6. The preparation method of claim 2, wherein the high performance liquid chromatography separation and purification of the step (4) is carried out by taking 52-55 v/v% methanol as a mobile phase, the flow rate is 20ml/min, a Zorbax PrepHT GF reversed phase preparation column with the flow rate of 21.2 x 250mm and 5 μm is taken as a stationary phase, the detection wavelength of an ultraviolet detector is 308nm, 50-200 mu L of chromatographic peaks are sampled each time, and the chromatographic peaks are collected for 34.8min and evaporated after accumulation for a plurality of times.
7. Use of a juniperidine sesquiterpene compound according to claim 1 for improving the aroma richness and softness of heated cigarettes and enhancing the sensation of fluid production.
CN202210798542.2A 2022-07-08 2022-07-08 Juniperidine sesquiterpene compound, preparation method and application thereof Active CN115073272B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210798542.2A CN115073272B (en) 2022-07-08 2022-07-08 Juniperidine sesquiterpene compound, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210798542.2A CN115073272B (en) 2022-07-08 2022-07-08 Juniperidine sesquiterpene compound, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115073272A CN115073272A (en) 2022-09-20
CN115073272B true CN115073272B (en) 2023-07-14

Family

ID=83258247

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210798542.2A Active CN115073272B (en) 2022-07-08 2022-07-08 Juniperidine sesquiterpene compound, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115073272B (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09107983A (en) * 1995-10-20 1997-04-28 Arakawa Chem Ind Co Ltd Production of hydroxymethylnaphthalenes and production of hydroxymethylmethylnaphthalenes and/or dihydroxymethylnaphthalenes
CN105884621B (en) * 2016-04-19 2017-12-29 秦瑞欣 A kind of sesquiterpenoids and its preparation method and application
CN105906491B (en) * 2016-04-20 2018-04-17 云南中烟工业有限责任公司 A kind of drop sesquiterpenoids, its preparation method and its application in cigarette humectation
CN106008219B (en) * 2016-05-20 2018-04-17 云南中烟工业有限责任公司 A kind of sesquiterpenoids, its preparation method and the application in anti-rotavirus medicaments are prepared
CN105924356B (en) * 2016-05-21 2018-04-03 云南省烟草农业科学研究院 A kind of sesquiterpenoids and its preparation method and application

Also Published As

Publication number Publication date
CN115073272A (en) 2022-09-20

Similar Documents

Publication Publication Date Title
CN105017190B (en) A kind of preparation method and application of benzo lactone compound in tobacco
CN106858710B (en) A kind of benzisoxa furfuran compound that can improve cigarette smoking effect and preparation method and application
CN105152880B (en) Nicotiana tabacum L. sesquiterpene-F prepared by a kind of supercritical fluid chromatography and application thereof
CN101538260B (en) Isoflavone compound and prepration method and application thereof
CN113087664B (en) Quinoline alkaloid compound and preparation method and application thereof
CN108912136B (en) Benzoisothiafuranone compound with effects of reducing thorns and promoting production of body fluid, and preparation method and application thereof
CN105061178B (en) A kind of sesquiterpenoidss, Preparation Method And The Use in Nicotiana tabacum L.
CN103554077B (en) Chromone compound as well as preparation method and application thereof
CN105175240B (en) Novel tobacco sesquiterpene H with antiviral activity is prepared with supercritical fluid chromatography
CN105001186B (en) A kind of preparation method and application of isopentene group benzo lactone compound in tobacco
CN106565649B (en) A kind of benzo lactone compound, preparation method and the application in cigarette filter flavoring
CN105085193B (en) A kind of sesquiterpene class compound, Preparation Method And The Use
CN101550083B (en) Benzo compounds in tobacco, preparation method and uses thereof
CN115073272B (en) Juniperidine sesquiterpene compound, preparation method and application thereof
CN106916160B (en) A kind of isobenzofuran class compounds process for production thereof that can improve cigarette suction comfort in pueraria lobata
CN105017198B (en) Preparation of isobutylene flavonoids in sun-cured tobacco and application of isobutylene flavonoids for resisting tobacco mosaic virus
CN115197054B (en) Sesquiterpene compound, preparation method and application thereof
CN104387361B (en) A kind of Isocoumarin compounds and its production and use
CN108033984B (en) Caffeic acid glucoside compound, preparation method and application thereof
CN104650053B (en) Flavonoids compound, as well as preparation method and applications thereof
CN114685524B (en) Chromone compound and preparation method and application thereof
CN106008219B (en) A kind of sesquiterpenoids, its preparation method and the application in anti-rotavirus medicaments are prepared
CN105777678B (en) A kind of 2 carbomethoxy furans flavouring immunomodulator compounds, its preparation method and its application in cigarette humectation
CN107382938B (en) Flavonoid compound capable of improving cigarette smoking throat comfort and preparation method and application thereof
CN107400107B (en) Flavonoid compound in rose waste residue and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant