CN105777678B - A kind of 2 carbomethoxy furans flavouring immunomodulator compounds, its preparation method and its application in cigarette humectation - Google Patents
A kind of 2 carbomethoxy furans flavouring immunomodulator compounds, its preparation method and its application in cigarette humectation Download PDFInfo
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- CN105777678B CN105777678B CN201610192666.0A CN201610192666A CN105777678B CN 105777678 B CN105777678 B CN 105777678B CN 201610192666 A CN201610192666 A CN 201610192666A CN 105777678 B CN105777678 B CN 105777678B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- 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
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- 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
- A24B15/36—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring
- A24B15/40—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring having only oxygen or sulfur as hetero atoms
- A24B15/403—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring having only oxygen or sulfur as hetero atoms having only oxygen as hetero atoms
- A24B15/406—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring having only oxygen or sulfur as hetero atoms having only oxygen as hetero atoms in a five-membered ring
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a kind of 2 carbomethoxy furfuran compounds, it has following structural formula：The compound is named as：The methyl formate of 5 (aminomethyl phenyl of 4 hydroxyl, 2 methoxyl group 6) 3 methylfuran 2, molecular formula C15H16O5.The invention also discloses the preparation method of 2 carbomethoxy furfuran compounds and its purposes in cigarette.
Description
Technical field
The invention belongs to technical field of tobacco chemistry, and in particular to a kind of 2- carbomethoxies furfuran compound, its preparation side
Method and its purposes in cigarette.
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 material just kind more than 3000, and also many compositions are still come from tobacco at present
Do not identify and.It has been widely recognized although Smoking is harmful to your health, tobacco still has by force to thousands of consumer
Big attraction, except nicotine it is additive in addition to, in tobacco enrich fragrance matter also play an important role.
Furfuran compound exists in many natural plants, and has multiple biological activities.According to the literature, such
Compound have it is antitumor, it is anti-oxidant, Ca2+ influx retardance, angiotensin-ii receptor antagonism, adenosine A l receptor antagonists, resist true
The pharmacological actions such as bacterium, antibacterial activity and platelet aggregation antagonism.Because Benzofurans compound has the pharmacology of such wide spectrum
Activity, domestic and international researcher conduct in-depth research to such compound, in addition to such compound is found from natural products,
Also obtain that there is more excellent active compound by structural modification.Simultaneously furfuran compound be also natural perfume material it is important into
Point, it is widely used from natural and synthesis furfuran compound in food and perfume industry.
Mainly using polyhydroxy substances such as glycerine, propane diols, sorbierites as humectant, humectant in China's cigarette industry
Main purpose in the moisture content of the pipe tobacco in process is maintained, improve the resist processing of pipe tobacco, but above-mentioned humectant into
There is very big associate in product smoking property of cigarette comfort level with its formulation composition and its blending.
The content of the invention
First aspect present invention is related to a kind of 2- carbomethoxies furfuran compound, and it has following structural formula：
The compound is named as：5- (4- hydroxyl -2- methoxyl group -6- aminomethyl phenyls) -3- methylfuran -2- formic acid first
Ester, molecular formula C15H16O5, it is light yellow gum thing.
Second invention of the invention is related to the preparation method that the 2- carbomethoxies furfuran compound is separated from drying cigarette, should
Method comprises the following steps：
(1) tobacco extract medicinal extract is prepared：Using airing tobacco as raw material, airing tobacco is crushed or is cut into segment, with the
One solvent soaking simultaneously extracts 3~5 times, each 24h~72h；Extract solution is merged, filtered and the tobacco extraction is obtained after concentrating
Thing medicinal extract；First solvent and the weight ratio of tobacco are (2-4):(4-6)；First solvent be selected from methanol, ethanol or
The mixture of acetone and water, when first solvent is methanol or the mixture of ethanol and water, wherein methanol or ethanol account for this
80wt%~100wt% of first solvent, when first solvent is the mixture of acetone and water, wherein acetone account for this first
60wt%~90wt% of solvent；
(2) silica gel column chromatography：The tobacco extract medicinal extract that step (1) is obtained and 160~300 mesh of its 2~4 times of weight
Silica gel mixing after dry column-packing, be then followed successively by 1 with volume ratio:0、20:1、9:1、8:2、7:3、6:4、1:1 and 1:2 chlorine
Imitative-acetone soln carries out gradient elution, will volume be wherein 6:The eluent obtained during 4 chloroform-acetone solution elution is referred to as
First eluent；
(3) high pressure liquid chromatography separates：The first eluent that step (2) obtains is passed through into high pressure liquid chromatography to be divided
From the high pressure liquid chromatography uses 21.2mm × 250mm, 5 μm of C18Chromatographic column, flow rate of mobile phase 20mL/min, flowing
It is mutually 38% methanol aqueous solution, UV-detector Detection wavelength is 312nm, each μ L of sample introduction 200 of the first eluent, is entered every time
Corresponding eluent is referred to as the second eluent when chromatographic peak retention time is 22.6min after sample, and second eluent is removed
Described 2- carbomethoxy furfuran compounds are obtained after solvent.
(4) purify：First is again dissolved in by the 2- carbomethoxies furfuran compound is obtained after the second eluent desolvation
Alcohol, and using methanol as mobile phase, chromatography, the 2- carbomethoxy furans chemical combination further purified are carried out by gel column
Thing.
Preferably, in the step of described preparation method (2), before being mixed with 160~300 mesh silica gel, first will
After the tobacco extract medicinal extract is dissolved with the second solvent of its 1.5~3 weight multiple and it is tobacco extract medicinal extract weight
0.8~1.2 times of 80~100 mesh silica gel mixed samples, second solvent are selected from methanol, ethanol or acetone.
Third aspect present invention is related to the use that described 2- carbomethoxies furfuran compound is used to improve cigarette smoking quality
On the way；
Preferably, the 2- carbomethoxies furfuran compound is used for the soft cigarette smoke together with humectant, improves flue gas
Mellow and full sense and comfortableness and the purposes for assigning cigarette smoke herbal.
Beneficial effects of the present invention：
1st, 2- carbomethoxy furfuran compounds of the invention are separated first that structure is novel.Correlation is not yet seen
Report.
2nd, 2- carbomethoxy furfuran compounds of the invention, show through cigarette addition experiment, it is with humectant suitably to compare
Example proportioning, having improves cigarette smoking quality effect, and there is good physics and sense organ humectation to act on to cigarette, improve flue gas
Mellow and full sense and comfortableness, also there is the effect for assigning cigarette smoke herbal.It can be seen that there is association between the compound and humectant
Same effect.The effect is in advance unexpected for those skilled in the art.
3rd, 2- carbomethoxies furfuran compound of the present invention is simple in construction, the guiding compound that can be researched and developed as tobacco aromaticss
And the new additive preparation for improving cigarette smoking quality is used in combination with humectant.
Brief description of the drawings
Fig. 1 is the carbon-13 nmr spectra of 2- carbomethoxies furfuran compound of the present invention；
Fig. 2 is the proton nmr spectra of 2- carbomethoxies furfuran compound of the present invention；
Fig. 3 is the main HMBC relevant indicators of 2- carbomethoxies furfuran compound of the present invention；
Fig. 4 is the structural formula of 2- carbomethoxies furfuran compound of the present invention.
Embodiment
The structure of the 2- carbomethoxy furfuran compounds of the present invention is to determine to come by the following method.Chemical combination of the present invention
Thing is light yellow gum thing；Ultraviolet spectra (solvent is methanol), λmax(logε)312(2.71)、246(3.26)、210(3.79)
nm；Infrared spectrum (pressing potassium bromide troche) νmax3415,2940,1716,1614,1570,1267,1128,1049cm-1；High-resolution
Mass spectrum (HRESIMS) provides quasi-molecular ion peak m/z 299.0900 [M+Na]+(calculated value 299.0895).With reference to1H and13CNMR spectrums provide a molecular formula C15H16O5, degree of unsaturation 8.Confirmed from the ir data of compound 1 in compound
There is ester carbonyl group (1716cm-1) and aromatic ring (1614,1570cm-1) functional group.The proton nmr spectra of compound is confirmed in compound
In the presence of 1 methoxyl group (δH3.80s), 1 METH (δH4.04), 3 fragrant methine (δH6.14s, 6.38s and
6.28s), two methyl (δH1.89s and 2.39s) and 1 phenolic hydroxyl group (δH10.59s).Its also confirming that of carbon-13 nmr spectra
Ester carbonyl group carbon (δ in compound be presentC162.2s), two methyl carbon (δC8.9q and 20.3q), a methoxyl group carbon (δC
56.0q), 3 fragrant methine carbon (δC105.3d, 100.2d and 108.4d), the quaternary carbon (δ of 4 sp2 oxidationsC 163.5s、
157.3s, 160.2s and 155.4s), and 3 sp2 fragrance quaternary carbons (δC102.6s, 112.4s and 136.9s).According to H3-13
(δHAnd C-2 (δ 1.89)C 163.5)、C-3(δC 102.6)、C-4(δCAnd C-12 (δ 105.3)C162.2), H-4 (δH
And C-2 (δ 6.14)C 163.5)、C-3(δC 102.6)、C-5(δC157.3) HMBC related (Fig. 3) confirms to deposit in compound
In 3- methyl -2- furancarboxylic acid ester structures.Further from H-4 (δHAnd C-6 (δ 6.14)C112.4) HMBC is related to confirm have
Phenyl ring is substituted in the C-5 positions of furan nucleus.The position of other substituents, another 1 methyl, which is substituted in C-11 positions, can pass through H3-14(δH
And C-6 (δ 2.39)C 112.4)、C-10(δCAnd C-11 (δ 108.4)C136.9) HMBC is related to be confirmed；Methoxy substitution exists
C-7 can be by methoxyl group hydrogen (δHAnd C-7 (δ 3.80)C160.2) HMBC is related to be determined；Phenolic hydroxyl group is substituted in C-9 positions can be by phenol hydroxyl
Base hydrogen (δHAnd C-8 (δ 10.59)C 100.2)、C-9(δCAnd C-10 (δ 155.4)C108.4) HMBC correlations are confirmed.
So far the structure of compound 1 is determined, and be named as 5- (4- hydroxyl -2- methoxyl group -6- aminomethyl phenyls) -3- methylfurans -
2- methyl formates.
The compound of table -1.1H NMR and13C NMR datas (C5D5N)
The compounds of this invention is separated first, is defined as 2- by above-mentioned nuclear magnetic resonance and measuring method of mass spectrum
Carbomethoxy furfuran compound, and characterize its concrete structure.Show through cigarette addition experiment：The compound has improvement cigarette
The purposes of suction quality, and can be used in combination with humectant, both increase the effect of flue gas herbal.The letter of the compounds of this invention structure
It is single, cigarette smoking quality can be obviously improved, can be used as the guiding compound of tobacco aromaticss research and development and combine with humectant makes
Prepared with 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 is any limitation as, based on present invention teach that any conversion or improvement made, each fall within protection scope of the present invention.
The present invention is raw materials used not to be limited by area and kind, and the tobacco in any source place can realize the present invention.Under
With the tobacco material of the 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 percetage by weight.In the examples where no specific technique or condition is specified,
Carried out according to the technology described by 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.Methanol refers to 100% methanol in the present invention, and ethanol refers to
100% ethanol, acetone refer to 100% acetone.
Embodiment 1
A kind of 2- carbomethoxies furfuran compound C15H18O4Preparation method, specifically include following steps：
(1) tobacco extract medicinal extract is prepared:Using airing tobacco as raw material, tobacco leaf is crushed or is cut into segment, and with first
Solvent soaking simultaneously extracts the tobacco leaf 4 times, each 54h, and extract solution is merged, filtered and the tobacco extract is obtained after concentrating
Medicinal extract；Wherein described first solvent is the mixture selected from methanol, the organic solvent of ethanol or acetone and water, when described first molten
When agent is methanol or the mixture of ethanol and water, wherein methanol or ethanol account for the 95wt% of first solvent, when described first molten
When agent is the mixture of acetone and water, wherein acetone accounts for the 70wt% of first solvent；And first solvent and tobacco weight ratio
For 3:5；
(2) silica gel column chromatography：By the tobacco extract medicinal extract with 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 the careless times of weight of extract medicinal extract 3, 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 6:4 chloroform-acetone is molten
The eluent that liquid obtains when eluting is referred to as the first eluent；
(3) high pressure liquid chromatography separates：Above-mentioned first eluent is passed through into high pressure liquid chromatography to be separated, the high pressure liquid
Phase chromatogram uses 21.2mm × 250mm, 5 μm of C18Chromatographic column, flow rate of mobile phase 20mL/min, mobile phase are 38% first
Alcohol, UV-detector Detection wavelength are 312nm, each μ L of sample introduction 200 of the first eluent, chromatographic peak retention time after each sample introduction
For 22.6min when corresponding eluent, referred to as the second eluent, the 2- first will be produced after the second eluent desolvation
Ester group furfuran compound.
(4) further purification：The 2- carbomethoxies furans that will be obtained afterwards in high pressure liquid chromatography separation
Compound is again dissolved in pure methanol, and using pure methanol as mobile phase, carries out chromatography by gel column, further purified
The 2- carbomethoxies furfuran compound.
Embodiment 2
For drying cigarette sample source used in Yunnan Yuxi, kind is Yuxi river and mountain cigarette.By tobacco leaf sampling 2.0kg crush with
95% methanol extracts 5 times, extracts 24h every time, and extract solution merges, and filtering, be concentrated under reduced pressure to obtain tobacco extract medicinal extract 95g.Will
The above-mentioned tobacco extract medicinal extract thick silica gel mixed sample of 100 mesh that 120g is used after the pure methanol dissolving of its 2.0 weight multiple, then with
Post is filled after 0.6kg 160 mesh silica gel mixing and carries out silica gel column chromatography, 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
6:4 chloroform-acetone elution fraction pacifies the prompt preparative high-performance liquid chromatographic of logical sequence 1,100 half separation, using 38% methanol as flowing
Phase, it is stationary phase that Zorbax SB-C18 (21.2 × 250mm, 5 μm), which prepare post, flow rate of mobile phase 20ml/min, ultraviolet detection
Device Detection wavelength is 312nm, each μ L of sample introduction 200, is collected corresponding when chromatographic peak retention time after each sample introduction is 22.6min
Eluent, it is repeatedly cumulative after desolvation；Products therefrom is dissolved with pure methanol again, then using pure methanol as mobile phase, is used
Sephadex LH-20 gel filtration chromatographies separate, and produce the 2- carbomethoxy furfuran compounds further purified.
Wherein, during gradient elution, during the elution of the mixed solvent of each ratio, it is eluted to untill no composition washes down, then
Change the mixed solvent of next ratio.
Embodiment 3
For drying cigarette sample source used in Dali, kind is that cigarette is stepped in Yunlong day.Tobacco leaf sampling 3.5kg is shredded, with
95% ethanol extracts 4 times, extracts 48h every time, and extract solution merges, and filtering, be concentrated under reduced pressure to obtain tobacco extract medicinal extract 245g.Will
The above-mentioned tobacco extract medicinal extract thick silica gel mixed sample of 80 mesh that 250g is used after the dissolving of the pure methanol of its 2.0 times of weight, then with 1.2kg
200 mesh silica gel mixing after fill post carry out silica gel column chromatography, with volume proportion be 1:0、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 6:4
Chloroform-acetone elution fraction pacifies the prompt preparative high-performance liquid chromatographic of logical sequence 1,100 half separation, using 38% methanol as mobile phase,
It is stationary phase that Zorbax SB-C18 (21.2 × 250mm, 5 μm), which prepare post, flow rate of mobile phase 20ml/min, UV-detector
Detection wavelength is 312nm, each μ L of sample introduction 200, is collected corresponding when chromatographic peak retention time after each sample introduction is 22.6min
Eluent, desolvation after repeatedly adding up；Products therefrom is dissolved with pure methanol again, then using pure methanol as mobile phase, is used
Sephadex LH-20 gel filtration chromatographies separate, and produce the 2- carbomethoxy furfuran compounds further purified.
Wherein, during gradient elution, during the elution of the mixed solvent of each ratio, it is eluted to untill no composition washes down, then
Change the mixed solvent of next ratio.
Embodiment 4
For drying cigarette sample source used in Kunming, Yunnan, kind is Songming safflower cigarette.Tobacco leaf sampling 5kg is crushed, with
75% acetone ultrasonic extraction 3 times, 72h is extracted every time, extract solution merges, and filtering, be concentrated under reduced pressure to obtain tobacco extract medicinal extract
385g.By the above-mentioned tobacco extract medicinal extract thick silica gel mixed sample of 90 mesh that 400g is used after the pure methanol dissolving of its 1.6 times of weight, then
Post is filled after being mixed with 2.4kg 180 mesh silica gel and carries out silica gel column chromatography, 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
For 6:4 chloroform-acetone elution fraction pacifies the prompt preparative high-performance liquid chromatographic of logical sequence 1,100 half separation, using 38% methanol as flowing
Phase, it is stationary phase that Zorbax SB-C18 (21.2 × 250mm, 5 μm), which prepare post, flow velocity 20ml/min, UV-detector detection
Wavelength is 312nm, each μ L of sample introduction 200, collects elution corresponding when chromatographic peak retention time after each sample introduction is 22.6min
Liquid, desolvation after repeatedly adding up；Products therefrom is dissolved with pure methanol again, then using pure methanol as mobile phase, uses Sephadex
LH-20 gel filtration chromatographies separate, and produce the 2- carbomethoxy furfuran compounds further purified.
Wherein, during gradient elution, during the elution of the mixed solvent of each ratio, it is eluted to untill no composition washes down, then
Change the mixed solvent of next ratio.
The identification of embodiment 5- compound structures
Compound prepared by Example 1, the structure for the 2- carbomethoxy furfuran compounds that method described above is prepared
It is measured by the following method.The compounds of this invention is light yellow gum thing；Ultraviolet spectra (solvent is methanol), λmax(log
ε)312(2.71)、246(3.26)、210(3.79)nm；Infrared spectrum (pressing potassium bromide troche) νmax 3415,2940,1716,
1614,1570,1267,1128,1049cm-1；High resolution mass spectrum (HRESIMS) provides [M of quasi-molecular ion peak m/z 299.0900
+Na]+(calculated value 299.0895).With reference to1H and13C H NMR spectroscopies provide a molecular formula C15H16O5, degree of unsaturation 8.From chemical combination
The ir data of thing 1 confirms there is ester carbonyl group (1716cm in compound-1) and aromatic ring (1614,1570cm-1) functional group.Change
The proton nmr spectra of compound confirms 1 methoxyl group (δ be present in compoundH3.80s), 1 METH (δH4.04), 3 virtues
Fragrant methine (δH6.14s, 6.38s and 6.28s), two methyl (δH1.89s and 2.39s) and 1 phenolic hydroxyl group (δH
10.59s).Its carbon-13 nmr spectra, which is also confirmed that in compound, has ester carbonyl group carbon (δC162.2s), two methyl carbon (δC 8.9q
And 20.3q), a methoxyl group carbon (δC56.0q), 3 fragrant methine carbon (δC105.3d, 100.2d and 108.4d), 4
Quaternary carbon (the δ of sp2 oxidationsC163.5s, 157.3s, 160.2s and 155.4s), and 3 sp2 fragrance quaternary carbons (δC 102.6s、
112.4s and 136.9s).According to H3-13(δHAnd C-2 (δ 1.89)C 163.5)、C-3(δC 102.6)、C-4(δC105.3) and
C-12(δC162.2), H-4 (δHAnd C-2 (δ 6.14)C 163.5)、C-3(δC 102.6)、C-5(δC157.3) HMBC is related
(figure -3) confirms 3- methyl -2- furancarboxylic acid ester structures be present in compound.Further from H-4 (δHAnd C-6 (δ 6.14)C
112.4) HMBC is related to confirm there are the C-5 positions that phenyl ring is substituted in furan nucleus.The position of other substituents, another 1 methyl substitution
It can pass through H in C-11 positions3-14(δHAnd C-6 (δ 2.39)C 112.4)、C-10(δCAnd C-11 (δ 108.4)C136.9)
HMBC is related to be confirmed；Methoxy substitution can be by methoxyl group hydrogen (δ in C-7HAnd C-7 (δ 3.80)C160.2) HMBC is related really
It is fixed；Phenolic hydroxyl group is substituted in C-9 positions can be by phenolic hydroxyl group hydrogen (δHAnd C-8 (δ 10.59)C 100.2)、C-9(δC155.4) and C-10
(δC108.4) HMBC correlations are confirmed.So far the structure of compound 1 is determined, and is named as 5- (4- hydroxyl -2- first
Epoxide -6- aminomethyl phenyls) -3- methylfuran -2- methyl formates.
Embodiment 6-8
The compound that respectively prepared by Example 2-4, is light yellow gum thing.Assay method is same as Example 5, confirms
Embodiment 2-4 prepare compound be 2- carbomethoxy furfuran compounds 5- (4- hydroxyl -2- methoxyl group -6- aminomethyl phenyls) -
3- methylfuran -2- methyl formates.
Embodiment 9- is added in cigarette and tested
The 2- carbomethoxies furfuran compound of any preparation in Example 1-4 carries out the perfuming effect experiment of cigarette, examination
It is as follows to test situation：
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 material as blank control.Above-mentioned 2- carbomethoxies furfuran compound is used
Ethanol water is made into 0.68% (m/v) solution, respectively with 5 μ L, 10 μ L, 15 μ L, 20 μ L, tetra- injection volume essence and flavoring agents
Injector is added in different " purple cloud and mist " Cigarette pipe tobaccos, then by cigarette sample in (22 ± 1) DEG C, relative humidity
48h is balanced under the conditions of 60% ± 2%, Cigarette A1, B1, C1 and D1 is respectively obtained, is smoked panel test for expert sensory.
The Cigarette and blank control cigarette that the 2- carbomethoxy furfuran compounds of the present invention will be with the addition of carry out sense organ
Quality evaluation, the results showed that, 2- carbomethoxies furfuran compound of the invention is used for cigarette flavouring upgrading positive effect, can be notable
Lift cigarette flavor concentration, increase perfume quantity, improve cigarette sense organ suction quality, there is wide application as cigarette additive
Prospect.
Embodiment 10- is used in combination with humectant in cigarette
The 2- carbomethoxies furfuran compound of any preparation in Example 1-4 enters them to cigarette sense organ product with humectant
The synergy experiment of matter, 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 material as blank control.Above-mentioned 2- carbomethoxies furfuran compound is used
Humectant is made into 0.68% (m/v) solution, is injected respectively with 5 μ L, 10 μ L, 15 μ L, 20 μ L, tetra- injection volumes with essence and flavoring agent
Machine is 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%, respectively obtains Cigarette A2, B2, C2 and D2.Above-mentioned 2- carbomethoxies furfuran compound is protected
Profit agent is made into 0.68% (m/v) solution, 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 it is separately added into the pipe tobacco of above-mentioned kinds of cigarettes cigarette and accounts for pipe tobacco
The humectant of quality 0.1%, 0.4%, 0.7%, 1%.Wherein described humectant can be in glycerine, propane diols or sorbierite
Any or their mixture.Then cigarette sample is balanced under the conditions of (22 ± 1) DEG C, relative humidity 60% ± 2%
48h.Respectively obtain Cigarette A3, B3, C3 and D3.
By the Cigarette for the 2- carbomethoxy furfuran compounds that with the addition of the present invention respectively while it with the addition of the present invention's
The Cigarette and blank control cigarette of 2- carbomethoxies furfuran compound and humectant carry out organoleptic quality evaluations, knot of smokeing panel test
Fruit shows：The compound and humectant are added in cigarette, there is good physics and sense organ humectation to act on to cigarette, Ji Nengrou
With cigarette smoke, the mellow and full sense of raising flue gas and comfortableness, also there is the effect for assigning cigarette smoke herbal.It can be seen that the chemical combination
There is synergy between thing and humectant.2- carbomethoxies furfuran compound is relative to the optimum addition of pipe tobacco 0.05 ‰
Between~0.15 ‰, humectant is relative to the optimum addition of pipe tobacco between 0.1%~0.7%.The compounds of this invention structure
Simply, cigarette smoking quality can be obviously improved, can be coordinated as the guiding compound of tobacco aromaticss research and development and with humectant
Prepared using the new additive for improving cigarette smoking quality.
Claims (5)
1. a kind of 2- carbomethoxies furfuran compound, it is characterised in that it has following structural formula：
The compound is named as：5- (4- hydroxyl -2- methoxyl group -6- aminomethyl phenyls) -3- methylfuran -2- methyl formates, point
Minor is C15H16O5。
2. the preparation method of the 2- carbomethoxy furfuran compounds described in a kind of claim 1, it is characterised in that this method includes
Following steps：
(1) tobacco extract medicinal extract is prepared：Using airing tobacco as raw material, airing tobacco is crushed or is cut into segment, it is molten with first
Agent is soaked and extracted 3~5 times, each 24h~72h；Extract solution is merged, filtered and the tobacco extract leaching is obtained after concentrating
Cream；First solvent and the weight ratio of tobacco are 2-4:4-6；First solvent is to be selected from methanol, ethanol or acetone and water
Mixture, when first solvent is methanol or the mixture of ethanol and water, wherein methanol or ethanol account for first solvent
80wt%~95wt%, when first solvent is the mixture of acetone and water, wherein acetone accounts for first solvent
60wt%~90wt%；
(2) silica gel column chromatography：The silicon of the tobacco extract medicinal extract that step (1) is obtained and 160~300 mesh of its 2~4 times of weight
Dry column-packing after glue mixing, 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-the third
Ketone solution carries out gradient elution, will volume be wherein 6:The eluent obtained during 4 chloroform-acetone solution elution is referred to as first and washed
De- liquid；
(3) high pressure liquid chromatography separates：The first eluent that step (2) obtains is passed through into high pressure liquid chromatography to be separated, institute
State high pressure liquid chromatography and use 21.2mm × 250mm, 5 μm of C18Chromatographic column, flow rate of mobile phase 20mL/min, mobile phase are
38% methanol aqueous solution, UV-detector Detection wavelength are 312nm, each μ L of sample introduction 200 of the first eluent, after each sample introduction
Chromatographic peak retention time eluent corresponding when being 22.6min is referred to as the second eluent, by the second eluent desolvation
Described 2- carbomethoxy furfuran compounds are obtained afterwards；
(4) purify：Methanol is again dissolved in by the 2- carbomethoxies furfuran compound is obtained after the second eluent desolvation, and
Using methanol as mobile phase, chromatography, the 2- carbomethoxy furfuran compounds further purified are carried out by gel column.
3. preparation method according to claim 2, it is characterised in that：In step (2), with 160~300 mesh silicon
Before glue mixing, with being carried for tobacco after first the tobacco extract medicinal extract is dissolved with the second solvent of its 1.5~3 weight multiple
80~100 mesh silica gel mixed samples of 0.8~1.2 times of thing medicinal extract weight are taken, second solvent is selected from methanol, ethanol or acetone.
4. the 2- carbomethoxies furfuran compound described in claim 1 is used for the purposes for improving cigarette smoking quality.
5. purposes according to claim 4, wherein the 2- carbomethoxies furfuran compound is for soft together with humectant
With cigarette smoke, the mellow and full sense of raising flue gas and comfortableness and the purposes for assigning cigarette smoke herbal.
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| CN114835693B (en) * | 2021-02-02 | 2024-01-23 | 湖北中烟工业有限责任公司 | Furanylpyrrole compound and preparation method and application thereof |
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| CN105017190A (en) * | 2015-06-25 | 2015-11-04 | 云南中烟工业有限责任公司 | Preparation method and use of benzolactone compound in tobacco |
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| CN105017190A (en) * | 2015-06-25 | 2015-11-04 | 云南中烟工业有限责任公司 | Preparation method and use of benzolactone compound in tobacco |
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| Title |
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| Three Novel Xanthones from Garcinia paucinervis and Their Anti-TMV Activity;Yu-Ping Wu，et al;《Molecules》;20130813;第18卷;第9663-9669页 * |
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