CN105384609B - Sesquiterpenoids and application thereof in tobacco is prepared with supercritical fluid chromatography - Google Patents
Sesquiterpenoids and application thereof in tobacco is prepared with supercritical fluid chromatography Download PDFInfo
- Publication number
- CN105384609B CN105384609B CN201510658485.8A CN201510658485A CN105384609B CN 105384609 B CN105384609 B CN 105384609B CN 201510658485 A CN201510658485 A CN 201510658485A CN 105384609 B CN105384609 B CN 105384609B
- Authority
- CN
- China
- Prior art keywords
- solvent
- tobacco
- cigarette
- sesquiterpenoid
- methanol
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/004—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from plant material or from animal material
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/18—Treatment of tobacco products or tobacco substitutes
- A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
- A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
- A24B15/302—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances by natural substances obtained from animals or plants
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/18—Treatment of tobacco products or tobacco substitutes
- A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
- A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
- A24B15/34—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a carbocyclic ring other than a six-membered aromatic ring
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B3/00—Preparing tobacco in the factory
- A24B3/12—Steaming, curing, or flavouring tobacco
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/23—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing six-membered aromatic rings and other rings, with unsaturation outside the aromatic rings
-
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The present invention is prepared for a kind of sesquiterpenoids of structure novel using supercritical fluid chromatography, which is 51,3 dihydro 1H indenes of (3 hydroxypropyl) 2,2,4 trimethyl, 7 alcohol, molecular formula C15H22O2, there are following structures.The invention also discloses the preparation methods and purposes of above compound.It is demonstrated experimentally that the sesquiterpenoids of the present invention has the purposes for improving cigarette smoking quality；It with humectant is matched in appropriate proportions simultaneously, there is good physics and sense organ humectation effect, and the comfort of the soft cigarette smoke of energy, raising cigarette smoke and the effect for assigning cigarette smoke herbal fragrance to cigarette.
Description
Technical field
The invention belongs to technical field of tobacco chemistry, and in particular to a kind of sesquiterpenoids extracted for the first time from tobacco
Compound.Meanwhile the preparation method the invention further relates to the compound and its purposes in cigarette smoking quality is improved.
Background technology
Tobacco is the plant that chemical composition is the most complicated in the world, and secondary metabolite is very abundant, by decades
Research, people identify the monomer chemistries substance come just more than more than 3000 kind from tobacco at present, but also there are many ingredient still
It does not identify and.It has been widely recognized although Smoking is harmful to your health, tobacco still has by force thousands of consumer
Big attraction, except nicotine it is additive in addition to, abundant fragrance matter also plays an important role in tobacco.
Sequiterpene (sesquiterpenes) refers to the natural terpenoids containing 15 carbon atoms in molecule.Sesquiterpenoids
Compound is distributed more widely, is often present in volatile oil in the form of alcohol, ketone, lactone etc. in plant, is higher boiling in volatile oil
Partial chief component.Have stronger fragrance and bioactivity, be medicine, food, cosmetics industry important original
Material.
Currently, mainly using the polyhydroxy substances such as glycerine, propylene glycol, sorbierite as humectant in China's cigarette industry,
The main purpose of humectant is the moisture content of pipe tobacco in maintenance process, improves the resist processing of pipe tobacco, but above-mentioned humectation
Agent sucks finished cigarettes also undesirable in comfort level, a kind of has the function of to improve cigarette smoking quality by isolated
Sesquiterpenoids, which is not yet seen relevant report, and coordinates the suction quality for improving cigarette with humectant
Also relevant report is had no.
Invention content
The purpose of the present invention is to provide a kind of new sesquiterpenoids.
It is a further object to provide a kind of methods for preparing the sesquiterpenoids.
The present invention also aims to provide purposes of the sesquiterpenoid in cigarette smoking quality is improved.
Unless otherwise indicated, the percentage employed in the present invention is weight percent.
First aspect present invention is related to a kind of sesquiterpenoids detached from tobacco, with following structural formula：
It is named as by IUPAC systematic nomenclatures：5- (3- hydroxypropyls) -2,2,4- trimethyl -1,3- dihydros -1H-
Indenes -7- alcohol.
The compound is light yellow gum object, its English name is named as 5- (3-hydroxypropyl) -2 by the present inventor,
2,4-trimethyl-1,3-dihydro-1H-inden-7-ol。
The second aspect of the present invention provides the preparation method of the sesquiterpenoids described in above-mentioned first aspect, the party
Method includes the following steps：
(1) tobacco extract medicinal extract is prepared:Using tobacco leaf as raw material, tobacco leaf is crushed or is cut into segment, and with the first solvent
It impregnates and extracts the tobacco leaf 3~5 times, every time for 24 hours~72h, extracting solution is merged, is filtered and the tobacco is obtained after concentrating carry
Take object medicinal extract；Wherein described first solvent is the mixture selected from methanol, the organic solvent of ethyl alcohol or acetone and water, when described the
When one solvent is methanol or the mixture of ethyl alcohol and water, wherein methanol or ethyl alcohol account for 80wt%~100wt% of first solvent,
When first solvent is the mixture of acetone and water, wherein acetone accounts for 60wt%~90wt% of first solvent；And the
One solvent：Tobacco=(2~4):1, weight ratio；
(2) silica gel column chromatography：After above-mentioned tobacco extract medicinal extract is mixed with 160~300 mesh silica gel of its 2-4 times of weight
Then dry column-packing is followed successively by 1 with volume ratio:0、20:1、9:1、8:2、7:3、6:4、1:1 and 1:2 chloroform-acetone solution into
Row gradient elution will volume be wherein 8:The eluent obtained during 2 chloroform-acetone solution elution is known as the first eluent；
(3) supercritical fluid chromatography isolates and purifies：Above-mentioned first eluent is passed through supercritical fluid chromatography to detach
Purifying, the supercritical fluid chromatography use 10mm × 150mm, 5 μm of Silica 2-EP chromatographic columns, mobile phase carbon dioxide/first
Alcohol (88/12%, mass ratio), flow rate of mobile phase 28mL/min, UV detector Detection wavelength be 250nm, the first eluent
Each 200~500 μ L of sample introduction of liquid collect eluent corresponding when chromatographic peak retention time is 10.20min after each sample introduction,
Referred to as the second eluent removes second eluent after solvent up to the sesquiterpenoid.
In a preferred embodiment of the present invention, the step of purifying further below is further included：It will be in the high pressure liquid
The sesquiterpenoid obtained after phase chromatographic isolation is again dissolved in pure methanol, and using pure methanol as mobile phase, by solidifying
Rubber column gel column carries out chromatography, the sesquiterpenoid further purified.
In a preferred embodiment of the present invention, in step (2), before being mixed with 160~300 mesh silica gel, first
By the dissolving of the second solvent selected from pure methanol, straight alcohol or pure acetone of its 1.5~3 times of weight of the tobacco extract medicinal extract
Afterwards with 80~100 mesh silica gel mixed samples of 0.8~1.2 times of weight for tobacco extract medicinal extract.
Third aspect present invention, which is related to the sesquiterpenoids described according to a first aspect of the present invention, is improving cigarette pumping
Inhale the purposes in quality.
Fourth aspect present invention is related to the sesquiterpenoids described according to a first aspect of the present invention for soft cigarette
Flue gas improves the mellow and full sense of cigarette smoke and comfort and/or the purposes for assigning cigarette smoke herbal fragrance.
Compared with prior art, the invention has the advantages that：The present invention sesquiterpenoids be for the first time by
It separates, structure novel.Show that it has the purposes for improving cigarette smoking quality through cigarette addition experiment, it can also be with guarantor
Profit agent matches in appropriate proportions, has good physics and sense organ humectation effect to cigarette, and can soft cigarette smoke, raising
The comfort of cigarette smoke and the effect for assigning cigarette smoke herbal fragrance.
Description of the drawings
Fig. 1 is the carbon-13 nmr spectra of sesquiterpenoids of the present invention；
Fig. 2 is the nuclear magnetic resonance spectroscopy of sesquiterpenoids of the present invention；
Fig. 3 is the main HMBC relevant indicators of sesquiterpenoids of the present invention.
Specific embodiment
The structure of sesquiterpenoids prepared by the present invention determines what is come by the following method.The compounds of this invention
For light yellow gum object；Ultraviolet spectra (solvent is methanol), λmax(log ε) 2210 (4.09), 250 (3.50) nm；Infrared spectrum
(pressing potassium bromide troche) νmax3382,2913,1602,1535,1450,1136,1063,865cm-1；High resolution mass spectrum (HRESIMS)
Provide quasi-molecular ion peak m/z 233.1546 [M-H]-(calculated value 233.1542).With reference to1H and13C H NMR spectroscopies provide one point
Minor C15H22O2, degree of unsaturation 5.Its infrared spectrum shows hydroxyl (3382cm-1) and phenyl ring (1602,1535,1450cm-1) functional group；Ultraviolet spectra has strong absorption at 250nm, also confirms that there are conjugated structures in compound.From1H and13CNMR is composed
(attribution data is shown in Table -1) signal can be seen that the phenyl ring replaced in compound there are one 1,2,3,4,5- five, a 3- hydroxyl third
Base, three methyl, two methylene, a quaternary carbon；The degree of unsaturation 4 of phenyl ring is removed, it should also be there are one ring in compound.According to
H-3 and C-2, C-4, C-8, C-9, C-13,14 and H-1 and C-2, C-3, C-7, C-8, C-13,14 HMBC are related (Fig. 3)
Susceptible of proof C-1, C-2, C-3 and C-13,5 yuan of carbocyclic rings of a gem-dimethyl are formd between 14 phenyl ring, which should be together with two
Methyl indane structure.After the parent nucleus of compound determines, remaining methyl, 3- hydroxypropyls and hydroxyl are the substitution on parent nucleus
Base.According to H-10 and C-4, C-5, C-6, H-11 susceptible of proof 3- hydroxypropyls related to the HMBC of C-5 are substituted in the C-5 of parent nucleus
Position；It is related to the HMBC of C-9 to C-4, C-5 according to H-15, it can be verified that the methyl is substituted in the C-4 positions of parent nucleus；According to phenolic hydroxyl group
Hydrogen is related to the HMBC of C-8 to C-6, C-7, it can be verified that phenolic hydroxyl group is substituted in the C-7 positions of parent nucleus.So far the structure of this compound obtains
To determine.
1. compound of table1H NMR and13C NMR datas (CCl3)
The compounds of this invention is separated for the first time, is determined as again by above-mentioned nuclear magnetic resonance and measuring method of mass spectrum
Half terpenoid, and characterize its concrete structure.Show through cigarette addition experiment：The compound has improvement cigarette smoking product
The purposes of matter can be also used cooperatively with humectant, can soft cigarette smoke, the comfort of cigarette smoke can also be improved, assign
The effect of cigarette smoke herbal fragrance.The compounds of this invention is simple in structure, can be obviously improved cigarette smoking quality, and cigarette can be used as fragrant
Expect the guiding compound of research and development and prepared with humectant with the use of the new additive for improving cigarette smoking quality.
The present invention is described in further detail with reference to the accompanying drawings and examples, but not in any way to the present invention
It limits, based on present invention teach that any transformation or improvement made, each fall within protection scope of the present invention.
The raw materials used in the present invention is not limited by area and kind, and the tobacco in any source place can realize the present invention, under
To derive from the tobacco material of cigarette industry Co., Ltd different sources in Yunnan, the present invention will be further described in face.Unless
It is otherwise noted, the percentage employed in the present invention is weight percent.In the examples where no specific technique or condition is specified,
It is carried out according to the described technology of document in the art or condition or according to product description.Agents useful for same or instrument are not noted
Bright production firm person, being can be by buying the conventional products obtained.If the solution in the present invention only gives solute, do not have
There is open solvent, then those skilled in the art should know that solvent is water.Pure methanol refers to 100% methanol, straight alcohol in the present invention
Refer to 100% ethyl alcohol, pure acetone refers to 100% acetone.
Embodiment 1
A kind of sesquiterpenoids C15H22O2Preparation method, specifically include following steps：
(1) tobacco extract medicinal extract is prepared：Using tobacco leaf as raw material, tobacco leaf is crushed or is cut into segment, and with the first solvent
It impregnates and extracts the tobacco leaf 4 times, each 54h, extracting solution is merged, is filtered and the tobacco extract leaching is obtained after concentrating
Cream；Wherein described first solvent is the mixture selected from methanol, the organic solvent of ethyl alcohol or acetone and water, when first solvent
During for the mixture of methanol or ethyl alcohol and water, wherein methanol or ethyl alcohol account for the 95wt% of first solvent, when first solvent
During for the mixture of acetone and water, wherein acetone accounts for the 70wt% of first solvent；And first solvent：Tobacco=3:1, weight
Than；
(2) silica gel column chromatography：By the tobacco extract medicinal extract its 2.5 times of weight selected from pure methanol, straight alcohol or
Pure acetone the second solvent dissolving after with for tobacco extract medicinal extract 1.2 times of weight 80~100 mesh silica gel mixed samples, then with cigarette
Dry column-packing after the 250 mesh silica gel mixing of careless 3 times of weight of extract medicinal extract, is then followed successively by 1 with volume ratio:0、20:1、9:1、
8:2、7:3、6:4、1:1 and 1:2 chloroform-acetone solution carries out gradient elution, will volume be wherein 8:2 chloroform-acetone is molten
The eluent that liquid obtains when eluting is known as the first eluent；
(3) supercritical fluid chromatography isolates and purifies：Above-mentioned first eluent is passed through supercritical fluid chromatography to detach
Purifying, the supercritical fluid chromatography use 10mm × 150mm, 5 μm of Silica 2-EP chromatographic columns, mobile phase carbon dioxide/first
Alcohol (88/12%, mass ratio), flow rate of mobile phase 28mL/min, UV detector Detection wavelength be 250nm, the first eluent
The each 200 μ L of sample introduction of liquid collect eluent corresponding when chromatographic peak retention time is 10.20min after each sample introduction, and referred to as the
Two eluents remove second eluent after solvent up to the sesquiterpenoid.
The preparation method further includes the step of purifying further below：It will be after supercritical fluid chromatography separation
The obtained sesquiterpenoid is again dissolved in pure methanol, and using pure methanol as mobile phase, and chromatography point is carried out by gel column
From the sesquiterpenoid further purified.
Embodiment 2
Tobacco sample used derives from Yunnan Yuxi, and kind is Yuxi K326.Tobacco leaf sampling 2.0kg is crushed with 95%
Methanol extracts 5 times, and for 24 hours, extracting solution merges for extraction every time, and tobacco extract medicinal extract 105g is concentrated under reduced pressure to obtain in filtering.By above-mentioned cigarette
The thick silica gel mixed sample of 100 mesh of 120g is used after the pure methanol dissolving of its 2.0 weight multiple of careless extract medicinal extract, then with 0.6kg's
Dress column carries out silica gel column chromatography after the mixing of 160 mesh silica gel, is 1 with volume proportion:0、20:1、9:1、8:2、7:3、6:4、1:1、1:
2 chloroform-acetone gradient elution, TLC monitorings merge identical part, obtain 8 parts, and wherein volume proportion is 8:2 chlorine
Imitative-acetone elution fraction is isolated and purified with supercritical fluid chromatography, which uses 10mm × 150mm, and 5
μm Silica 2-EP chromatographic columns, mobile phase carbon dioxide/methanol (88/12%, mass ratio), flow rate of mobile phase 28mL/
Min, UV detector Detection wavelength are 250nm, and each 200 μ L of sample introduction, chromatographic peak retention time is after collecting each sample introduction
Corresponding eluent during 10.20min removes solvent after repeatedly adding up；Products therefrom is dissolved again with pure methanol, then with pure first
Alcohol is mobile phase, is detached with Sephadex LH-20 gel filtration chromatographies to get the sesquiterpenoid further purified.
Wherein, it during gradient elution, during the elution of the mixed solvent of each ratio, is eluted to until no ingredient washes down, then
Change the mixed solvent of next ratio.
Embodiment 3
Tobacco sample used derives from Dali, and kind is cloud and mist 200.Tobacco leaf sampling 3.5kg is shredded, with 95%
Ethyl alcohol extracts 4 times, extracts 48h every time, and extracting solution merges, and tobacco extract medicinal extract 250g is concentrated under reduced pressure to obtain in filtering.It will be above-mentioned
The thick silica gel mixed sample of 80 mesh of 250g is used after the pure methanol dissolving of its 2.0 times of weight of tobacco extract medicinal extract, then with 1.2kg's
Dress column carries out silica gel column chromatography after the mixing of 200 mesh silica gel, is 1 with volume proportion:0、20:1、9:1、8:2、7:3、6:4、1:1、1:
2 chloroform-acetone gradient elution, TLC monitorings merge identical part, obtain 8 parts, and wherein volume proportion is 8:2 chlorine
Imitative-acetone elution fraction is isolated and purified with supercritical fluid chromatography, which uses 10mm × 150mm, and 5
μm Silica 2-EP chromatographic columns, mobile phase carbon dioxide/methanol (88/12%, mass ratio), flow rate of mobile phase 28mL/
Min, UV detector Detection wavelength are 250nm, and each 200 μ L of sample introduction, chromatographic peak retention time is after collecting each sample introduction
Corresponding eluent during 10.20min removes solvent after repeatedly adding up；Products therefrom is dissolved again with pure methanol, then with pure first
Alcohol is mobile phase, is detached with Sephadex LH-20 gel filtration chromatographies to get the sesquiterpenoid further purified.
Wherein, it during gradient elution, during the elution of the mixed solvent of each ratio, is eluted to until no ingredient washes down, then
Change the mixed solvent of next ratio.
Embodiment 4
Tobacco sample used derives from Kunming, Yunnan, and kind is the big gold dollar of safflower.Tobacco leaf sampling 5kg is crushed, with 75%
Acetone ultrasonic extraction 3 times, extract 72h every time, extracting solution merges, and tobacco extract medicinal extract 380g is concentrated under reduced pressure to obtain in filtering.
It will use the thick silica gel mixed sample of 90 mesh of 400g after the pure methanol dissolving of above-mentioned tobacco extract medicinal extract its 1.6 times of weight, then with
Dress column carries out silica gel column chromatography after the 180 mesh silica gel mixing of 2.4kg, is 1 with volume proportion:0、20:1、9:1、8:2、7:3、6:
4、1:1、1:2 chloroform-acetone gradient elution, TLC monitorings merge identical part, obtain 8 parts, wherein volume proportion is
8:2 chloroform-acetone elution fraction is isolated and purified with supercritical fluid chromatography, the supercritical fluid chromatography using 10mm ×
150mm, 5 μm of Silica 2-EP chromatographic columns, mobile phase carbon dioxide/methanol (88/12%, mass ratio), flow rate of mobile phase is
28mL/min, UV detector Detection wavelength are 250nm, and each 200 μ L of sample introduction collect chromatographic peak retention time after each sample introduction
Corresponding eluent during for 10.20min removes solvent after repeatedly adding up；Products therefrom is dissolved again with pure methanol, then with pure
Methanol is mobile phase, is detached with Sephadex LH-20 gel filtration chromatographies to get the sesquiterpenoid further purified.
Wherein, it during gradient elution, during the elution of the mixed solvent of each ratio, is eluted to until no ingredient washes down, then
Change the mixed solvent of next ratio.
The identification of embodiment 5- compound structures
Compound prepared by Example 1, the structure of the sesquiterpenoids determine what is come by the following method；Change
Conjunction object is light yellow gum object；Ultraviolet spectra (solvent is methanol), λmax(log ε) 2210 (4.09), 250 (3.50) nm；It is infrared
Spectrum (pressing potassium bromide troche) νmax3382,2913,1602,1535,1450,1136,1063,865cm-1；High resolution mass spectrum
(HRESIMS) quasi-molecular ion peak m/z 233.1546 [M-H] is provided-(calculated value 233.1542).With reference to1H and13C H NMR spectroscopies
Provide a molecular formula C15H22O2, degree of unsaturation 5.Its infrared spectrum shows hydroxyl (3382cm-1) and phenyl ring (1602,
1535,1450cm-1) functional group；Ultraviolet spectra has strong absorption at 250nm, also confirms that there are conjugated structures in compound.From1H
With13CNMR spectrum (attribution data is shown in Table -1) signals can be seen that the phenyl ring replaced in compound there are one 1,2,3,4,5- five, one
A 3- hydroxypropyls, three methyl, two methylene, a quaternary carbon；The degree of unsaturation 4 of phenyl ring is removed, should also be had in compound
One ring.According to H-3 and C-2, C-4, C-8, C-9, C-13,14 and H-1 and C-2, C-3, C-7, C-8, C-13,14
HMBC correlation (Fig. 3) susceptible of proof C-1, C-2, C-3 and C-13 forms 5 yuan of carbocyclic rings of a gem-dimethyl, the change between 14 phenyl ring
It closes object and should be gem-dimethyl indane structure.After the parent nucleus of compound determines, remaining methyl, 3- hydroxypropyls and hydroxyl are mother
Substituent group on core.According to H-10 and C-4, C-5, C-6, H-11 susceptible of proof 3- hydroxypropyls related to the HMBC of C-5 are substituted in
The C-5 positions of parent nucleus；It is related to the HMBC of C-9 to C-4, C-5 according to H-15, it can be verified that the methyl is substituted in the C-4 positions of parent nucleus；Root
It is related to the HMBC of C-8 to C-6, C-7 according to phenolic hydroxyl group hydrogen, it can be verified that phenolic hydroxyl group is substituted in the C-7 positions of parent nucleus.So far this compound
Structure be determined.
Embodiment 6-8
The compound that respectively prepared by Example 2-4 is yellow jelly.Assay method is same as Example 5, confirms real
It is sesquiterpenoids 5- (3- hydroxypropyls) -2,2,4- trimethyl -2,3- dihydros -1H- to apply compound prepared by 2-4
Indenes -7- alcohol.
Embodiment 9- flavorings are tested
The sesquiterpenoids of any preparation in Example 1-4 carries out the perfuming effect experiment of cigarette, test situation
It is as follows：
It is Hong Yun Red River group product " purple cloud and mist " Cigarette for addition cigarette, the pipe tobacco weight of every is 0.68g.
To be not added with " purple cloud and mist " Cigarette of any other substance as blank control.By above-mentioned sesquiterpenoids ethanol water
Solution is made into the solution of 0.68% (m/v), respectively with 5 μ L, 10 μ L, 15 μ L, 20 μ L, tetra- injection volume essence and flavoring agent injectors
Added in different " purple cloud and mist " Cigarette pipe tobaccos, then by cigarette sample (22 ± 1) DEG C, relative humidity 60% ±
48h is balanced under the conditions of 2%, Cigarette A1, B 1, C1 and D1 is respectively obtained, smokes panel test for expert sensory.
The Cigarette for the sesquiterpenoids for being added to the present invention and blank control cigarette are carried out organoleptic quality to comment
Valency, the results showed that, sesquiterpenoids of the invention is with obvious effects for cigarette flavouring upgrading, can be obviously improved cigarette flavor
Concentration increases perfume quantity, improves cigarette sense organ suction quality, has broad application prospects as cigarette additive.
The synergistic effect of embodiment 10- and humectant
The sesquiterpenoids of any preparation and humectant are into their associations to cigarette sensory quality in Example 1-4
Same effect test, test situation are as follows：
It is Hong Yun Red River group product " purple cloud and mist " Cigarette for addition cigarette, the pipe tobacco weight of every is 0.68g.
To be not added with " purple cloud and mist " Cigarette of any other substance as blank control.By above-mentioned sesquiterpenoids humectant
The solution of 0.68% (m/v) is made into, is added respectively with 5 μ L, 10 μ L, 15 μ L, 20 μ L, tetra- injection volumes essence and flavoring agent injector
To in different " purple cloud and mist " Cigarette pipe tobaccos, then by cigarette sample in (22 ± 1) DEG C, relative humidity 60% ± 2%
48h is balanced under part, respectively obtains Cigarette A2, B2, C2 and D2.Above-mentioned sesquiterpenoids is made into humectant
The solution of 0.68% (m/v) is added to not respectively with 5 μ L, 10 μ L, 15 μ L, 20 μ L, tetra- injection volumes essence and flavoring agent injector
In same " purple cloud and mist " Cigarette pipe tobacco, then it is separately added into the pipe tobacco of above-mentioned kinds of cigarettes cigarette and accounts for tobacco quality
0.1%th, 0.4%, 0.7%, 1% humectant.Wherein described humectant can be any in glycerine, propylene glycol or sorbierite
Kind or their mixture.Then cigarette sample is balanced into 48h under the conditions of (22 ± 1) DEG C, relative humidity 60% ± 2%.Point
Cigarette A3, B3, C3 and D3 are not obtained.
By the Cigarette for the sesquiterpenoids for being added to the present invention respectively while it is added to sequiterpene of the invention
The Cigarette and blank control cigarette of class compound and humectant carry out organoleptic quality evaluations, and smoking result shows：It is rolling up
The compound and humectant are added in cigarette, to cigarette have good physics and sense organ humectation effect, can soft cigarette smoke,
Mellow and full sense and the comfort of flue gas are improved, also there is the effect for assigning cigarette smoke herbal fragrance.It can be seen that the compound and humectant
Between have synergy.Sesquiterpenoids between 0.05 ‰~0.15 ‰, is protected relative to the optimum addition of pipe tobacco
Profit agent is relative to the optimum addition of pipe tobacco between 0.1%~0.7%.The compounds of this invention is simple in structure, can be obviously improved
Cigarette smoking quality, can be as the guiding compound that tobacco aromaticss are researched and developed and with humectant with the use of improvement cigarette smoking
It is prepared by the new additive of quality.
Claims (4)
1. a kind of preparation method of sesquiterpenoid, the preparation method include the following steps：
The structural formula of the sesquiterpenoid is as follows：The compound is named as：5- (3- hydroxypropyls) -2,2,4- trimethyls -
1,3- dihydro -1H- indenes -7- alcohol, molecular formula C15H22O2；
(1) tobacco extract medicinal extract is prepared：Using tobacco leaf as raw material, tobacco leaf is crushed or is cut into segment, and with the first solvent
It impregnates and extracts the tobacco leaf 3~5 times, every time for 24 hours~72h, extracting solution is merged, is filtered and the tobacco is obtained after concentrating carry
Take object medicinal extract；Wherein described first solvent is the mixture selected from methanol, the organic solvent of ethyl alcohol or acetone and water, when described the
When one solvent is methanol or the mixture of ethyl alcohol and water, wherein methanol or ethyl alcohol account for 80wt%~100wt% of first solvent,
When first solvent is the mixture of acetone and water, wherein acetone accounts for 60wt%~90wt% of first solvent；And the
One solvent：Tobacco=(2-4):(4-6), weight ratio；
(2) silica gel column chromatography：By above-mentioned tobacco extract medicinal extract its 1.5~3 times of weight selected from pure methanol, straight alcohol or pure
80~120 mesh silica gel mixed samples after the second solvent dissolving of acetone with 0.8~1.2 times of weight for tobacco extract medicinal extract, then
Dry column-packing after being mixed with 160~300 mesh silica gel of its 2-4 times of weight, is then followed successively by 1 with volume ratio:0、20:1、9:1、8:
2、7:3、6:4、1:1 and 1:2 chloroform-acetone solution carries out gradient elution, will volume be wherein 8:2 chloroform-acetone solution
The eluent obtained during elution is known as the first eluent；
(3) supercritical fluid chromatography isolates and purifies：Above-mentioned first eluent is passed through supercritical fluid chromatography to isolate and purify,
The supercritical fluid chromatography uses 10mm × 150mm, 5 μm of Silica 2-EP chromatographic columns, mobile phase carbon dioxide/methanol matter
Amount is than for 88/12, flow rate of mobile phase 28mL/min, and UV detector Detection wavelength is 250nm, each sample introduction of the first eluent
200~500 μ L collect eluent corresponding when chromatographic peak retention time is 10.20min after each sample introduction, and referred to as second washes
De- liquid removes second eluent after solvent up to the sesquiterpenoid.
2. the preparation method according to claim 1, it is characterised in that：It further includes the step of purifying further below：It will
Be again dissolved in pure methanol in the sesquiterpenoid that obtains later of supercritical fluid chromatography separation, and using pure methanol as
Mobile phase carries out chromatography, the sesquiterpenoid further purified by gel column.
3. a kind of sesquiterpenoid is used to improve the purposes of cigarette smoking quality, the structural formula of the sesquiterpenoid is such as
Under：The compound is named as：- 2,2,4- trimethyl -1,3- dihydro -1H- indenes -7- alcohol of 5- (3- hydroxypropyls), molecular formula are
C15H22O2；
4. purposes according to claim 3, for soft cigarette smoke, the comfort of raising cigarette smoke and/or imparting
Cigarette smoke herbal fragrance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510658485.8A CN105384609B (en) | 2015-10-13 | 2015-10-13 | Sesquiterpenoids and application thereof in tobacco is prepared with supercritical fluid chromatography |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510658485.8A CN105384609B (en) | 2015-10-13 | 2015-10-13 | Sesquiterpenoids and application thereof in tobacco is prepared with supercritical fluid chromatography |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105384609A CN105384609A (en) | 2016-03-09 |
| CN105384609B true CN105384609B (en) | 2018-06-12 |
Family
ID=55417442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510658485.8A Active CN105384609B (en) | 2015-10-13 | 2015-10-13 | Sesquiterpenoids and application thereof in tobacco is prepared with supercritical fluid chromatography |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105384609B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105949065B (en) * | 2016-05-20 | 2018-05-18 | 云南中烟工业有限责任公司 | A kind of sesquiterpenoids, its preparation method and its application in resisting tobacco mosaic virus drug is prepared |
| 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 |
| CN106117062B (en) * | 2016-06-24 | 2018-05-18 | 云南中烟工业有限责任公司 | A kind of preparation method of Phenylpropanoid Glycosides class fumet and its use in conjunction with cigarette humectant |
-
2015
- 2015-10-13 CN CN201510658485.8A patent/CN105384609B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| synthesis of (+/-)-pterosin-M and ontitin;B Raju et al.;《Indian journal of chemistry》;19871031;第26B卷;page 914-916 * |
| Synthetic Investigations on Illudinine: A New Synthesis of Methyl 8-Methoxy-2,2-dimethyl-7-oxo-1,2,3,5,6,7- hexahydro-s-indacene-4-carboxylate;Talupuru Girija et al.;《J. CHEM. SOC. PERKIN TRANS. 1》;19911231;page: 1467-1471 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105384609A (en) | 2016-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105061178B (en) | A kind of sesquiterpenoidss, Preparation Method And The Use in Nicotiana tabacum L. | |
| CN105017190B (en) | A kind of preparation method and application of benzo lactone compound in tobacco | |
| CN105384609B (en) | Sesquiterpenoids and application thereof in tobacco is prepared with supercritical fluid chromatography | |
| CN105481818B (en) | A kind of flavouring humectation isocoumarin class compound and its preparation method and application | |
| CN105152880B (en) | Nicotiana tabacum L. sesquiterpene-F prepared by a kind of supercritical fluid chromatography and application thereof | |
| CN106858710B (en) | A kind of benzisoxa furfuran compound that can improve cigarette smoking effect and preparation method and application | |
| CN105175239B (en) | Sesquiterpenoid compound capable of inhibiting activity of tobacco mosaic virus in tobacco, preparation method and applications thereof | |
| CN105949065B (en) | A kind of sesquiterpenoids, its preparation method and its application in resisting tobacco mosaic virus drug is prepared | |
| CN106380473B (en) | A kind of lactone compound, preparation method and use | |
| CN105001186B (en) | A kind of preparation method and application of isopentene group benzo lactone compound in tobacco | |
| CN105175240B (en) | Novel tobacco sesquiterpene H with antiviral activity is prepared with supercritical fluid chromatography | |
| CN105085193B (en) | A kind of sesquiterpene class compound, Preparation Method And The Use | |
| CN106565649B (en) | A kind of benzo lactone compound, preparation method and the application in cigarette filter flavoring | |
| CN105777678B (en) | A kind of 2 carbomethoxy furans flavouring immunomodulator compounds, its preparation method and its application in cigarette humectation | |
| CN106083782B (en) | A kind of benzo lactone compound, preparation method and its application in cigarette filter flavoring | |
| CN107700278A (en) | A kind of cigarette paper additive with sweet larynx effect and its application | |
| CN107467712A (en) | It is a kind of with the tobacco sauce additive of antibacterial activity and its application | |
| CN105906491B (en) | A kind of drop sesquiterpenoids, its preparation method and its application in cigarette humectation | |
| CN106083781B (en) | A kind of benzo lactone preparation method and applications with cigarette flavouring effect | |
| CN107366194B (en) | It is a kind of to have effects that the cigarette paper additive of pharynx-clearing throat-benefiting and its application | |
| CN107759554A (en) | A kind of hydroxypropyl isoflavonoid and its preparation method and application | |
| CN105837412B (en) | A kind of sesquiterpenoids, its preparation method and its application in resisting tobacco mosaic virus medicine is prepared | |
| CN104650053B (en) | Flavonoids compound, as well as preparation method and applications thereof | |
| CN107778275B (en) | Isoflavone compound extracted from rose waste residue and preparation method and application thereof | |
| CN106565449B (en) | A kind of preparation method and application for the chalcone compounds can increase cigarette smoking sweet tea sense |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |