CN102311465A - Monosaccharide geraniol carbonate monoester compound and preparation method and application thereof - Google Patents
Monosaccharide geraniol carbonate monoester compound and preparation method and application thereof Download PDFInfo
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- CN102311465A CN102311465A CN201110260085A CN201110260085A CN102311465A CN 102311465 A CN102311465 A CN 102311465A CN 201110260085 A CN201110260085 A CN 201110260085A CN 201110260085 A CN201110260085 A CN 201110260085A CN 102311465 A CN102311465 A CN 102311465A
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- geraniol
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- 0 CC(C)=CCCC(C)=CCOC(OC(C(*OC1CO)O)[C@@]1O)=O Chemical compound CC(C)=CCCC(C)=CCOC(OC(C(*OC1CO)O)[C@@]1O)=O 0.000 description 1
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- 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
Abstract
The invention relates to a cigarette humectant, discloses a monosaccharide geraniol carbonate monoester compound, also discloses a preparation method of the compound, and tests the moisture retention, damp resistance and perfume sustained release effect of the compound as a cigarette humectant. Tests demonstrate that the monosaccharide geraniol carbonate monoester compound has moisture retention performance for tobacco, and has the effect of aroma increase, uniform aroma release, and cigarette sensory quality improvement. In the formula, O-R represent residues of five-carbon monosaccharide or six-carbon monosaccharide; geraniol carbonyl is located at any possible position of the five-carbon or six-carbon monosaccharide.
Description
Technical field
The invention belongs to technical field of tobacco, relate to one type of monose ester cigarette humectant, be specifically related to monose Geraniol carbonic acid monoester class compound, its preparation method and conduct thereof and have the application that the humectation performance has the new cigarette humectant of flavouring and the effect of slowly-releasing spices concurrently.
Background technology
Flavouring humectation and cigarette quality are in close relations." tobacco industry Eleventh Five-Year Plan program for the development of science and technology " and " the medium-term and long-term science and technology development planning outline (2006-2020) of tobacco industry " spells out, and flavouring humectation technical study is one of main direction of industry science and technology coming years research and scientific and technical innovation.
The ideal humectant should have physics humectation and sense organ humectation function concurrently.The physics humectation is promptly preserved moisture, refer to keep pipe tobacco in the course of processing water ratio, improve the anti-processibility of pipe tobacco and keep the water ratio of finished cigarettes; The sense organ humectation then is meant and improves the smoking property of cigarette comfort level, as reducing flue gas drying sense and pungency, improving pleasant impression etc.The humectant that adopts in China's production of cigarettes at present is mainly polyhydroxy substances such as Ucar 35, glycerine, sorbyl alcohol; But it is really not satisfactory that it is kept the finished cigarettes water ratio and improves the effect of sucking comfort level; As hour in relative humidity; There are problems such as moisture in cut tobacco scatters and disappears comparatively fast, main flume moisture is on the low side, pungency is bigger than normal, dry sensation is obvious; And when relative humidity was big, this type of humectant can not stop the taken in excess of moisture, and the too high cigarette of moisture content is prone to macula lutea even goes mouldy.
The ideal sweetener should possess stable in properties, release characteristics such as perfume is even, high safety.The present compound that the sweetener major part is lower as molecular weight, boiling point is low, volatility is stronger that uses of perfuming cigarette exists to be prone in the high temperature process process volatilely between loss, shelf lives release disadvantages such as perfume is inhomogeneous when losing fragrance, suction.
Therefore, research and development have the novel humectant that better humectation performance has flavouring and the effect of slowly-releasing spices concurrently, and humectation performance and the international competitiveness that improves China's cigarette product had important practical significance.
Summary of the invention
The object of the present invention is to provide a kind of monose Geraniol carbonic acid monoester class compound.
Second purpose of the present invention is to disclose the preparation method of such monose Geraniol carbonic acid monoester class compound.
The 3rd purpose of the present invention is to disclose such monose Geraniol carbonic acid monoester class compound as having the purposes that the humectation performance has the new cigarette humectant of flavouring and the effect of slowly-releasing spices concurrently.
The objective of the invention is to realize like this:
A kind of monose Geraniol carbonic acid monoester class compound with following general formula:
Wherein, O-R represents the residue of five carbon monose or six carbon monose; The Geraniol carbonyl is positioned at any possible position of five carbon or six carbon monose.
Above-mentioned five carbon monose are preferably from wood sugar, ribose, pectinose, lyxose, ribulose or xylulose; Six carbon monose are preferably from glucose, semi-lactosi, seminose, sorbose, gulose, fructose, N.F,USP MANNITOL, sorbyl alcohol, 1; 4-anhydrous sorbitol or 3, the 6-anhydrous sorbitol.
Second purpose of the present invention is achieved in that
A kind of preparation method of aforesaid monose Geraniol carbonic acid monoester class compound, available following method preparation:
In the reaction formula, the protection base of
expression monose;
With the Geraniol is starting raw material, and it is dissolved in the suitable solvent, adds alkali and chlorine formylation reagent, after reaction for some time, through aftertreatment, makes chloroformic acid spiceleaf alcohol ester; Then in suitable solvent and under the acid binding agent existence condition; Chloroformic acid spiceleaf alcohol ester and five carbon monose or six carbon monose direct reaction; Through aftertreatment; Make the mixture of corresponding monose Geraniol carbonic acid monoester class compound and monose Geraniol carbonic acid polyester compounds,, promptly get corresponding monose Geraniol carbonic acid monoester class compound through conventional recrystallization or column chromatography purification.
Also can be in suitable solvent and under the acid binding agent existence condition with the chloroformic acid spiceleaf alcohol ester that makes; Five carbon monose or the reaction of six carbon monose with band protection base; The gained Geraniol carbonyl-basic monose carbonic acid of protection monoester class compound deprotection base under conditions suitable gets corresponding monose Geraniol carbonic acid monoester class compound.
Its concrete preparation method is described below:
Steps A): with the Geraniol is starting raw material, and it is dissolved in the suitable solvent, adds alkali and chlorine formylation reagent react, gets chloroformic acid spiceleaf alcohol ester; Wherein, chlorine formylation reaction solvent for use is selected from: C
3-8Alkanone, C
5-10Fat alkane or naphthenic hydrocarbon, N, dinethylformamide, ether, isopropyl ether, MTBE, THF, glycol dimethyl ether, sherwood oil, C
1-6Lipid acid and C
1-6Ester that Fatty Alcohol(C12-C14 and C12-C18) forms, methylene dichloride, chloroform, 1; 2-ethylene dichloride, toluene or acetonitrile, reaction can be carried out in single solvent, also can in two kinds of mixed solvents, carry out; The volume ratio of two kinds of mixed solvents is 1: 0.1～10, and preferred solvent is: methylene dichloride, chloroform, acetone or toluene;
Chlorine formylation reacts used alkali: basic metal or alkaline earth metal hydroxides, basic metal or alkaline earth metal carbonate, basic metal or alkali metal bicarbonates, piperidines, Pyrrolidine, triethylamine, Tributylamine, trioctylamine, pyridine, N; N-dimethyl--α-Ben Yian, N-methylmorpholine, N-methyl piperidine, triethylene diamine, 1; 8-diazabicyclo [5; 4,0] combination of 11 carbon-7-alkene or above-mentioned various alkali, preferred bases is: sodium hydrogencarbonate, triethylamine or pyridine;
Used chlorine formylation reagent is: phosgene, superpalite or two (trichloromethyl) carbonic ether;
The molar feed ratio of Geraniol, chlorine formylation reagent and alkali is 1.0: 0.2～10.0: 0.5～20.0, and preferred molar feed ratio is 1.0: 0.3～2.0: 1.0～6.0; Temperature of reaction is-40 ℃～130 ℃, and preferable reaction temperature is-20 ℃～40 ℃; Reaction times is 20 minutes～48 hours, and the preferred reaction time is 1 hour～24 hours.
Step B): by steps A the chloroformic acid spiceleaf alcohol ester that) obtains is in suitable solvent and under the acid binding agent existence condition; With five carbon monose or six carbon monose direct reaction; Get the mixture of corresponding monose Geraniol carbonic acid monoester class compound and monose Geraniol carbonic acid polyester compounds; Through conventional recrystallization or column chromatography purification, get corresponding monose Geraniol carbonic acid monoester class compound;
Wherein, the reaction solvent for use is selected from: C
3-8Alkanone, C
5-10Fat alkane or naphthenic hydrocarbon, N, dinethylformamide, ether, isopropyl ether, MTBE, THF, glycol dimethyl ether, sherwood oil, C
1-6Lipid acid and C
1-6Ester that Fatty Alcohol(C12-C14 and C12-C18) forms, methylene dichloride, chloroform, 1; 2-ethylene dichloride, toluene, N-Methyl pyrrolidone, DMSO 99.8MIN., water, pyridine or acetonitrile; Reaction can be carried out in single solvent, also can in two kinds of mixed solvents, carry out, and the volume ratio of two kinds of mixed solvents is 1: 0.1～10; Preferred solvent is: THF, N, dinethylformamide, methylene dichloride, ETHYLE ACETATE or pyridine;
Used acid binding agent is: triethylamine, Tributylamine, trioctylamine, pyridine, N; N-dimethyl--α-Ben Yian, TBAH, basic metal or alkaline earth metal hydroxides, basic metal or alkaline earth metal carbonate, basic metal or alkali metal bicarbonates, preferred acid binding agent is: triethylamine, pyridine or sodium hydrogencarbonate;
The molar feed ratio of five carbon monose or six carbon monose and chloroformic acid spiceleaf alcohol ester is 1.0: 0.2～10.0, and preferred molar feed ratio is 1.0: 1.0～3.0; The molar feed ratio of acid binding agent and chloroformic acid spiceleaf alcohol ester is 1.0～10.0: 1.0, and preferred molar feed ratio is 1.0～3.0: 1.0; Temperature of reaction is-40 ℃～90 ℃, and preferable reaction temperature is-20 ℃～40 ℃; Condensation reaction time is 1 hour～48 hours, and the preferred reaction time is 3 hours～24 hours.
Step C): also can be with by steps A the chloroformic acid spiceleaf alcohol ester that) obtains in suitable solvent with the acid binding agent existence condition under, with the five carbon monose or the reaction of six carbon monose of band protection base, the corresponding Geraniol carbonyl-basic monose carbonic acid of protection monoester class compound;
Wherein, the reaction solvent for use is selected from: C
3-8Alkanone, C
5-10Fat alkane or naphthenic hydrocarbon, N, dinethylformamide, ether, isopropyl ether, MTBE, THF, glycol dimethyl ether, sherwood oil, C
1-6Lipid acid and C
1-6Ester that Fatty Alcohol(C12-C14 and C12-C18) forms, methylene dichloride, chloroform, 1; 2-ethylene dichloride, toluene, N-Methyl pyrrolidone, DMSO 99.8MIN., water, pyridine or acetonitrile; Reaction can be carried out in single solvent, also can in two kinds of mixed solvents, carry out, and the volume ratio of two kinds of mixed solvents is 1: 0.1～10; Preferred solvent is: THF, N, dinethylformamide, methylene dichloride, ETHYLE ACETATE or pyridine;
Used acid binding agent is: triethylamine, Tributylamine, trioctylamine, pyridine, N; N-dimethyl--α-Ben Yian, TBAH, basic metal or alkaline earth metal hydroxides, basic metal or alkaline earth metal carbonate, basic metal or alkali metal bicarbonates, preferred acid binding agent is: triethylamine, pyridine or sodium hydrogencarbonate;
The five carbon monose of band protection base or the molar feed ratio of six carbon monose and chloroformic acid spiceleaf alcohol ester are 1.0: 0.2～10.0, and preferred molar feed ratio is 1.0: 1.0～3.0; The molar feed ratio of acid binding agent and chloroformic acid spiceleaf alcohol ester is 1.0～10.0: 1.0, and preferred molar feed ratio is 1.0～3.0: 1.0; Temperature of reaction is-40 ℃～90 ℃, and preferable reaction temperature is-20 ℃～40 ℃; Condensation reaction time is 1 hour～48 hours, and the preferred reaction time is 3 hours～24 hours.
Step D): by step C the Geraniol carbonyl that) obtains-basic monose carbonic acid of protection monoester class compound deprotection base under conditions suitable gets corresponding monose Geraniol carbonic acid monoester class compound; Wherein, The used acid of deprotection base is: content is that 10%～95% trifluoroacetic acid aqueous solution, content are that 10%～95% aqueous formic acid, content are that 10%～95% acetic acid aqueous solution or content are 1%～37% aqueous hydrochloric acid, and preferred acid is: content is that 50%～90% trifluoroacetic acid aqueous solution, content are that 50%～95% aqueous formic acid, content are that 50%～95% acetic acid aqueous solution or content are 10%～37% aqueous hydrochloric acid; The consumption of acid and the ratio of the Geraniol carbonyl-basic monose carbonic acid of protection monoester class compound are: 0.5～50.0: 1.0 (L/mol), and preferred feed ratio is 0.5～10.0: 1.0 (L/mol); Temperature of reaction is-40 ℃～90 ℃, and preferable reaction temperature is-20 ℃～40 ℃; Condensation reaction time is 1 hour～48 hours, and the preferred reaction time is 2 hours～24 hours.
The 3rd purpose of the present invention is achieved in that
The disclosed monose Geraniol of the present invention carbonic acid monoester class compound can be used as the cigarette humectant; This compounds has certain water-soluble and fat-soluble; Be the non-ionic type glycosyl surfactant active; Can stablize the cigarette water ratio through the bilayer protective membrane of being separated by, reach the effect of humectation, protection against the tide, slowly-releasing spices and flavouring at tobacco surface formation profit.
Compared with prior art, beneficial effect of the present invention is following:
1, the disclosed monose Geraniol of the present invention carbonic acid monoesters class cigarette humectant can have humectation and moistureproof two kinds of effects simultaneously through the bilayer protective membrane of being separated by at tobacco surface formation profit; The speed that in the exsiccant climatope, dries out through the tobacco that this type humectant was handled is slow; And the speed that in the climatope of humidity, absorbs moisture is also slow, can effectively slow down the variation of tobacco moisture with envrionment conditions.
2, the disclosed monose Geraniol of the present invention carbonic acid monoesters class cigarette humectant also can be separated by the bilayer protective membrane and the volatilization that significantly slow down flavour ingredient in the tobacco through the profit that forms on tobacco surface, thereby has certain slowly-releasing spices effect.
3, the fragrance of the disclosed monose Geraniol of the present invention carbonic acid monoesters class cigarette humectant own is less or do not have fragrance, but in the result of combustion of tobacco process, can hot crackedly discharge the characteristic aroma component, makes the more comfortable harmony of fragrance of cigarette.Saccharide compound itself is present in the tobacco, and Geraniol is widely used in the actual production as the cigarette deodorant tune, and therefore, the present invention's disclosed this type cigarette humectant and tobacco have compatibleness preferably, and be safe.
4, with present tobacco industry on widely used Ucar 35 or glycerine compare, the product toxicological harmless after the burning of the disclosed monose Geraniol of the present invention carbonic acid monoesters class cigarette humectant, safe in utilization, more help the security of sucking of tobacco, be easy to apply.
Embodiment
Can further describe the present invention through following embodiment, yet scope of the present invention is not limited to following embodiment.One of skill in the art can understand, and under the prerequisite that does not deviate from the spirit and scope of the present invention, can carry out various variations and modification to the present invention.
Embodiment 1: chloroformic acid spiceleaf alcohol ester synthetic
In reaction flask, add 2000ml CH
2Cl
2With two (trichloromethyl) carbonic ether 129g (0.44mol), after stirring at room to solid entirely dissolves, reaction flask is put during cryosel bathes, be cooled to-10 ℃ after; Add Geraniol 1.28mol, after the dissolving, drip the 200ml pyridine fully, the control rate of addition; Make reacting liquid temperature maintain 0～5 ℃, drip and finish, reaction solution is warming up to room temperature naturally, stirring reaction spends the night; Promptly get the dichloromethane solution of chloroformic acid spiceleaf alcohol ester, need not purifying and promptly can be used for step reaction down, quantitative yield.
Embodiment 2: chloroformic acid spiceleaf alcohol ester synthetic
Operating process just substitutes two (trichloromethyl) carbonic ethers with embodiment 1 with superpalite, pyridine substitutes with sodium hydrogencarbonate, CH
2Cl
2Substitute with toluene, get the toluene solution of chloroformic acid spiceleaf alcohol ester, need not purifying and promptly can be used for step reaction down, quantitative yield.
The preparation of embodiment 3:3-O-Geraniol carbonyl-D-glucopyanosyl ester (compound I)
Get the chloroformic acid spiceleaf alcohol ester dichloromethane solution 0.06mol that embodiment 1 makes; Be added dropwise to be cooled to-5～0 ℃ 1,2:5 is in 6-two-O-isopropylidene-D-grape furanose 0.05mol, triethylamine 0.08mol and the methylene dichloride 100ml mixed solution; Stirring at room reaction 20h; Reaction changes reaction solution in the separating funnel over to after finishing, and organic layer is used 5%HCl aqueous solution 25ml, saturated NaHCO successively
3Aqueous solution 25ml and saturated NaCl aqueous solution 25ml washing are through anhydrous Na
2SO
4Drying is filtered, and removes solvent under reduced pressure; Add 70% trifluoroacetic acid aqueous solution 50ml in the resistates, 15～25 ℃ of stirring reaction 3h remove solvent under reduced pressure; Gained 3-O-Geraniol carbonyl-D-glucopyanosyl ester bullion through purification by silica gel column chromatography (elutriant: chloroform: methyl alcohol=20: 1, v/v), collect the product component; Remove solvent under reduced pressure, get 3-O-Geraniol carbonyl-D-glucopyanosyl ester white foam body, yield 55.0%; HR-TOFMS (+Q) m/z:383.1680 ([C
17H
28O
8+ Na]
+Calculated value: 383.1682).
The preparation of embodiment 4:6-O-Geraniol carbonyl-D-gala pyrans sugar ester (compound I I)
Operating process is with 1 with embodiment 3,2:5; 6-two-O-isopropylidene-D-grape furanose is with 1,2:3, and 4-two-O-isopropylidene-D-gala pyranose substitutes; Methylene dichloride substitutes with toluene, and triethylamine substitutes with pyridine, and 70% trifluoroacetic acid aqueous solution substitutes with 80% aqueous formic acid; Get 6-O-Geraniol carbonyl-D-gala pyrans sugar ester white foam body, yield 75.0%; HR-TOFMS (+Q) m/z:383.1675 ([C
17H
28O
8+ Na]
+Calculated value: 383.1682).
The preparation of embodiment 5:2-O-Geraniol carbonyl-D-gala pyrans sugar ester (compound III) and 3-O-Geraniol carbonyl-D-gala pyrans sugar ester (compound IV)
The compound III compound IV
Operating process is with 1 with embodiment 3,2:5; 6-two-O-isopropylidene-D-grape furanose is with 4, and 6-O-isopropylidene-D-semi-lactosi methyl glucoside substitutes, and 70% trifluoroacetic acid aqueous solution substitutes with 20% aqueous hydrochloric acid; (elutriant: chloroform/methanol=10/1 v/v), gets 2-O-Geraniol carbonyl-D-gala pyrans sugar ester to bullion through purification by silica gel column chromatography; Yield 28.0%, HR-TOFMS (+Q) m/z:383.1688 ([C
17H
28O
8+ Na]
+Calculated value: 383.1682); Obtain 3-O-Geraniol carbonyl-D-gala pyrans sugar ester simultaneously, yield 32.0%, HR-TOFMS (+Q) m/z:383.1679 ([C
17H
28O
8+ Na]
+Calculated value: 383.1682).
The preparation of embodiment 6:4-O-Geraniol carbonyl-D-mannopyranose ester (compound V) and 6-O-Geraniol carbonyl-D-mannopyranose ester (compound VI)
Compound V compound VI
Operating process is with 1 with embodiment 3,2:5; 6-two-O-isopropylidene-D-grape furanose is with 2, and 3-O-isopropylidene-D-seminose methyl glucoside substitutes, and 70% trifluoroacetic acid aqueous solution substitutes with 20% aqueous hydrochloric acid; (elutriant: chloroform/methanol=10/1 v/v), gets 4-O-Geraniol carbonyl-D-mannopyranose ester to bullion through purification by silica gel column chromatography; Yield 18.0%, HR-TOFMS (+Q) m/z:383.1677 ([C
17H
28O
8+ Na]
+Calculated value: 383.1682); Obtain 6-O-Geraniol carbonyl-D-mannopyranose ester simultaneously, yield 53.0%, HR-TOFMS (+Q) m/z:383.1680 ([C
17H
28O
8+ Na]
+Calculated value: 383.1682).
The preparation of embodiment 7:2-O-Geraniol carbonyl-D-mannopyranose ester (compound VI I) and 3-O-Geraniol carbonyl-D-mannopyranose ester (compound VIII)
Compound VI I compound VIII
Operating process is with 1 with embodiment 3,2:5; 6-two-O-isopropylidene-D-grape furanose is with 4, and 6-O-isopropylidene-D-seminose methyl glucoside substitutes, and 70% trifluoroacetic acid aqueous solution substitutes with 20% aqueous hydrochloric acid; (elutriant: chloroform/methanol=10/1 v/v), gets 2-O-Geraniol carbonyl-D-mannopyranose ester to bullion through purification by silica gel column chromatography; Yield 27.0%, HR-TOFMS (+Q) m/z:383.1689 ([C
17H
28O
8+ Na]
+Calculated value: 383.1682); Obtain 3-O-Geraniol carbonyl-D-mannopyranose ester simultaneously, yield 36.0%, HR-TOFMS (+Q) m/z:383.1685 ([C
17H
28O
8+ Na]
+Calculated value: 383.1682).
The preparation of embodiment 8:1-O-Geraniol carbonyl-D-fruit pyrans sugar ester (compound I X)
Operating process is with embodiment 3, and just with 1,2:5,6-two-O-isopropylidene-D-grape furanose are with 2, and 3:4,5-two-O-isopropylidene-D-really pyranose substitute, and gets 1-O-Geraniol carbonyl-D-fruit pyrans sugar ester white foam body, yield 60.0%; HR-TOFMS (+Q) m/z:383.1686 ([C
17H
28O
8+ Na]
+Calculated value: 383.1682).
The preparation of embodiment 9:3-O-Geraniol carbonyl-D-fruit pyrans sugar ester (compounds X)
Operating process is with embodiment 3, and just with 1,2:5,6-two-O-isopropylidene-D-grape furanose are with 1, and 2:4,5-two-O-isopropylidene-D-really pyranose substitute, and gets 3-O-Geraniol carbonyl-D-fruit pyrans sugar ester white foam body, yield 55.0%; HR-TOFMS (+Q) m/z:383.1680 ([C
17H
28O
8+ Na]
+Calculated value: 383.1682).
The preparation of embodiment 10:1-O-Geraniol carbonyl-D-sorb pyrans sugar ester (compounds X I)
Get the chloroformic acid spiceleaf alcohol ester toluene solution 0.06mol that embodiment 2 makes, be added dropwise to the D-sorbose 0.05mol, pyridine 0.08mol and the N that are cooled to-5～0 ℃, in the dinethylformamide 100ml mixed solution; Stirring at room reaction 20h; After reaction finishes, filter and separate out solid, filtrate decompression is steamed and is desolventized; Resistates is dissolved in methylene dichloride 200ml, and organic layer is used 5%HCl aqueous solution 25ml, saturated NaHCO successively
3Aqueous solution 25ml and saturated NaCl aqueous solution 25ml washing are through anhydrous Na
2SO
4Drying is filtered, and removes solvent under reduced pressure; Gained 1-O-Geraniol carbonyl-D-sorb pyrans sugar ester bullion is through purification by silica gel column chromatography (elutriant: chloroform/methanol=10/1; V/v), collect the product component, remove solvent under reduced pressure; Get 1-O-Geraniol carbonyl-D-sorb pyrans sugar ester white foam body, yield 38.0%; HR-TOFMS (+Q) m/z:383.1690 ([C
17H
28O
8+ Na]
+Calculated value: 383.1682).
The preparation of the ancient Lip river pyrans sugar ester of embodiment 11:6-O-Geraniol carbonyl-D-(compounds X II)
Operating process just substitutes the D-sorbose with embodiment 10 with the D-gulose, get the ancient Lip river of 6-O-Geraniol carbonyl-D-pyrans sugar ester white foam body, yield 25.0%; HR-TOFMS (+Q) m/z:383.1684 ([C
17H
28O
8+ Na]
+Calculated value: 383.1682).
The preparation of embodiment 12:1-O-Geraniol carbonyl-Nitranitol (compounds X III)
Operating process just substitutes the D-sorbose with embodiment 10 with N.F,USP MANNITOL, get 1-O-Geraniol carbonyl-Nitranitol white foam body, yield 36.0%; HR-TOFMS (+Q) m/z:385.1840 ([C
17H
30O
8+ Na]
+Calculated value: 385.1838).
The preparation of embodiment 13:1-O-Geraniol carbonyl-sorbitol ester (compounds X IV)
Operating process just substitutes the D-sorbose with embodiment 10 with sorbyl alcohol, get 1-O-Geraniol carbonyl-sorbitol ester white foam body, yield 33.0%; HR-TOFMS (+Q) m/z:385.1835 ([C
17H
30O
8+ Na]
+Calculated value: 385.1838).
The preparation of embodiment 14:5-O-Geraniol carbonyl-D-wood furans sugar ester (compounds X V)
Operating process is with embodiment 3, and just with 1,2:5,6-two-O-isopropylidene-D-grape furanose are with 1, and 2-O-isopropylidene-D-wood furanose substitutes, and gets 5-O-Geraniol carbonyl-D-wood furans sugar ester white foam body, yield 48.0%; HR-TOFMS (+Q) m/z:353.1573 ([C
16H
26O
7+ Na]
+Calculated value: 353.1576).
Embodiment 15:6-O-Geraniol carbonyl-1, the preparation of 4-sorbitan ester (compounds X VI)
Operating process is with embodiment 10, just with the D-sorbose with 1, the 4-anhydrous sorbitol substitutes, must 6-O-Geraniol carbonyl-1,4-sorbitan ester white foam body, yield 70-0%; HR-TOFMS (+Q) m/z:367.1731 ([C
17H
28O
7+ Na]
+Calculated value: 367.1733).
Embodiment 16:1-O-Geraniol carbonyl-3, the preparation of 6-sorbitan ester (compounds X VII)
Operating process is with embodiment 10, just with the D-sorbose with 3, the 6-anhydrous sorbitol substitutes, must 1-O-Geraniol carbonyl-3,6-sorbitan ester white foam body, yield 65.0%; HR-TOFMS (+Q) m/z:367.1738 ([C
17H
28O
7+ Na]
+Calculated value: 367.1733).
The preparation of embodiment 17:5-O-Geraniol carbonyl-D-nuclear furans sugar ester (compounds X VIII)
Operating process just substitutes the D-sorbose with embodiment 10 with D-ribose, get 5-O-Geraniol carbonyl-D-nuclear furans sugar ester white foam body, yield 45.0%; HR-TOFMS (+Q) m/z:353.1570 ([C
16H
26O
7+ Na]
+Calculated value: 353.1576).
The preparation of embodiment 18:5-O-Geraniol carbonyl-D-arbinofuranose ester (compounds X IX)
Operating process just substitutes the D-sorbose with embodiment 10 with the D-pectinose, get 5-O-Geraniol carbonyl-D-arbinofuranose ester white foam body, yield 40.0%; HR-TOFMS (+Q) m/z:353.1572 ([C
16H
26O
7+ Na]
+Calculated value: 353.1576).
The preparation of embodiment 19:5-O-Geraniol carbonyl-D-lysol furans sugar ester (compounds X X)
Operating process just substitutes the D-sorbose with embodiment 10 with the D-lyxose, get 5-O-Geraniol carbonyl-D-lysol furans sugar ester white foam body, yield 52.0%; HR-TOFMS (+Q) m/z:353.1574 ([C
16H
26O
7+ Na]
+Calculated value: 353.1576).
The preparation of embodiment 20:1-O-Geraniol carbonyl-D-ribulose ester (compounds X XI)
Operating process just substitutes the D-sorbose with embodiment 10 with the D-ribulose, get 1-O-Geraniol carbonyl-D-ribulose ester white foam body, yield 35.0%; HR-TOFMS (+Q) m/z:353.1571 ([C
16H
26O
7+ Na]
+Calculated value: 353.1576).
The preparation of embodiment 21:1-O-Geraniol carbonyl-D-xylulose ester (compounds X XII)
Operating process just substitutes the D-sorbose with embodiment 10 with the D-xylulose, get 1-O-Geraniol carbonyl-D-xylulose ester white foam body, yield 40.0%; HR-TOFMS (+Q) m/z:353.1582 ([C
16H
26O
7+ Na]
+Calculated value: 353.1576).
The preparation of embodiment 22:1-O-Geraniol carbonyl-D-glucopyanosyl ester (compounds X XIII), 2-O-Geraniol carbonyl-D-glucopyanosyl ester (compounds X XIV) and 6-O-Geraniol carbonyl-D-glucopyanosyl ester (compounds X XV)
Compounds X XIII compounds X XIV compounds X XV
Operating process is with embodiment 10, just the D-sorbose substituted with D-glucose, must 1-O-Geraniol carbonyl-D-glucopyanosyl ester white foam body, and yield 15.0%, HR-TOFMS (+Q) m/z:383.1687 ([C
17H
28O
8+ Na]
+Calculated value: 383.1682); Obtain 2-O-Geraniol carbonyl-D-glucopyanosyl ester white foam body simultaneously, yield 10.0%, HR-TOFMS (+Q) m/z:383.1676 ([C
17H
28O
8+ Na]
+Calculated value: 383.1682); Also obtain 6-O-Geraniol carbonyl-D-glucopyanosyl ester white foam body simultaneously, yield 52.0%, HR-TOFMS (+Q) m/z:383.1680 ([C
17H
28O
8+ Na]
+Calculated value: 383.1682).
Embodiment 23: humectation and moisture-proof role test
Is contrast with blank pipe tobacco with the pipe tobacco that adds Ucar 35, to above-mentioned five carbon or six carbon monose Geraniol carbonic acid monoester class compounds (I～XXV) the humectation effect of pipe tobacco has been carried out the experiment contrast.Aqueous ethanolic solution with 50% is a solvent, and above-claimed cpd and Ucar 35 are mixed with solution and evenly spray in the blank pipe tobacco (addition be pipe tobacco weight 0.4%) respectively, sprays into the solvent of equivalent in the blank pipe tobacco.After each tobacco sample behind the application of sample being placed the climatic chamber balance 48h of 22 ℃ of relative humidity 60%, temperature; Every kind of pipe tobacco is got 4 increments; Every part of 10g; 2 parts of parallel appearance wherein are positioned in the encloses container of 22 ℃ of relative humidity 45%, temperature, two parts of parallel appearance are positioned in the encloses container of 22 ℃ of relative humidity 85%, temperature in addition; Every 24h weighs 1 time, surveys periodic water ratio according to calculating each part pipe tobacco with the weight differential of initial weight and initial aqueous rate; Measure the average that the result gets 2 parallel appearance, and make the time dependent curve of water ratio; Measure the dehydration always continue to each part pipe tobacco or suction and reach in a basic balancely, the result sees table 1 (" RH " representative " relative humidity " in the table).
Table 1 humectation and moistureproof test result
Test result shows; Under the condition of 22 ℃ of relative humidity 45%, temperature; The equilibrium moisture content of above-mentioned Geraniol carbonic acid monoester class compound is higher than Ucar 35 contrast pipe tobacco or blank pipe tobacco in various degree; And under the condition of 22 ℃ of relative humidity 85%, temperature; The equilibrium moisture content of above-mentioned monose ester compound is lower than Ucar 35 contrast pipe tobacco or blank pipe tobacco in various degree, shows that disclosed five carbon of the present invention or six carbon monose Geraniol carbonic acid monoester class compounds have humectation preferably and moisture-proof role to pipe tobacco.
Embodiment 24: slowly-releasing spices effect test
Tobacco sample to add Ucar 35 is contrast, to above-mentioned five carbon or six carbon monose Geraniol carbonic acid monoester class compounds (I～XXV) the slowly-releasing spices effect of pipe tobacco has been carried out the experiment contrast.After above-mentioned monose ester compound solution and propylene glycol solution being sprayed in the pipe tobacco (addition be pipe tobacco weight 0.4%) respectively and placing certain hour, 0.5 gram of taking a sample respectively is that solvent carries out supersound extraction with the methylene dichloride; Dichloromethane solution after the extraction utilizes the content of flavor matter in the gas chromatograph-mass spectrometer analysis filtrating behind filtering with microporous membrane.
Test result shows; The content of typical flavor matter all is higher than the tobacco sample that Ucar 35 was handled in various degree in the tobacco sample that above-mentioned monose ester compound was handled, and shows that disclosed five carbon of the present invention or six carbon monose Geraniol carbonic acid monoester class compounds have certain flavour ingredient evaporable effect in the pipe tobacco that slows down.
Embodiment 25: the thermo-cracking composition is analyzed
Adopt online thermal cracking-gas chromatograph-mass spectrometric hyphenated technique, (the thermo-cracking composition of I～XXV) is studied to above-mentioned five carbon or six carbon monose Geraniol carbonic acid monoester class compounds.Take by weighing about 0.2mg sample respectively, place solid sampler, under 200 ℃, 450 ℃ and 700 ℃, carry out the moment cracking, the cracking atmosphere is a helium, and split product is directly imported in the GCMS by helium and carries out qualitative analysis.
Mensuration result shows, these compounds all have aroma component such as Geraniol to produce at 200 ℃, 450 ℃ and 700 ℃, show that disclosed five carbon of the present invention or six carbon monose Geraniol carbonic acid monoester class compounds have the effect that thermo-cracking discharges aroma component.
Embodiment 26: the sensory evaluating smoking estimates
For disclosed five carbon of the present invention or six carbon monose Geraniol carbonic acid monoester class compound (I～XXV), carried out sensory evaluating smoking's evaluation with following method.
Aqueous ethanolic solution with 50% is a solvent; Above-claimed cpd and Ucar 35 are mixed with solution and evenly spray in the blank pipe tobacco (addition be pipe tobacco weight 0.4%) respectively; Each tobacco sample behind the application of sample is placed the climatic chamber balance 48h of 22 ℃ of relative humidity 60%, temperature; Process cigarette, put into balance 48h under the condition of 22 ℃ of relative humidity 60%, temperature again, it is carried out sensory evaluating smoking's evaluation by panel of experts.
Smoking result shows; Compare with Ucar 35 contrast cigarette; The cigarette flavor amount of having added above-mentioned monose ester compound increases, releases fragrant even, good with the fragrant Harmony of cigarette; The aesthetic quality be improved significantly, showing that disclosed five carbon of the present invention or six carbon monose Geraniol carbonic acid monoester class compounds have increases perfume quantity, releases the fragrant all even effect that improves the cigarette aesthetic quality.
Claims (9)
1. one type of monose Geraniol carbonic acid monoester class compound with following general formula:
In the general formula, O-R represents the residue of five carbon monose or six carbon monose; The Geraniol carbonyl is positioned at any possible position of five carbon or six carbon monose.
2. monose Geraniol carbonic acid monoester class compound as claimed in claim 1; It is characterized in that; Above-mentioned five carbon monose are selected from: wood sugar, ribose, pectinose, lyxose, ribulose or xylulose; Six carbon monose are selected from: glucose, semi-lactosi, seminose, sorbose, gulose, fructose, N.F,USP MANNITOL, sorbyl alcohol, 1,4-anhydrous sorbitol or 3,6-anhydrous sorbitol.
3. according to claim 1 or claim 2 monose Geraniol carbonic acid monoester class compound is characterized in that said compound is selected from: 3-O-Geraniol carbonyl-D-glucopyanosyl ester; 6-O-Geraniol carbonyl-D-gala pyrans sugar ester, 2-O-Geraniol carbonyl-D-gala pyrans sugar ester, 3-O-Geraniol carbonyl-D-gala pyrans sugar ester; 4-O-Geraniol carbonyl-D-mannopyranose ester, 6-O-Geraniol carbonyl-D-mannopyranose ester, 2-O-Geraniol carbonyl-D-mannopyranose ester; 3-O-Geraniol carbonyl-D-mannopyranose ester, 1-O-Geraniol carbonyl-D-fruit pyrans sugar ester, 3-O-Geraniol carbonyl-D-fruit pyrans sugar ester; 1-O-Geraniol carbonyl-D-sorb pyrans sugar ester, the ancient Lip river of 6-O-Geraniol carbonyl-D-pyrans sugar ester, 1-O-Geraniol carbonyl-Nitranitol; 1-O-Geraniol carbonyl-sorbitol ester, 5-O-Geraniol carbonyl-D-wood furans sugar ester, 6-O-Geraniol carbonyl-1; The 4-sorbitan ester, 1-O-Geraniol carbonyl-3,6-sorbitan ester; 5-O-Geraniol carbonyl-D-nuclear furans sugar ester, 5-O-Geraniol carbonyl-D-arbinofuranose ester, 5-O-Geraniol carbonyl-D-lysol furans sugar ester; 1-O-Geraniol carbonyl-D-ribulose ester; 1-O-Geraniol carbonyl-D-xylulose ester, 1-O-Geraniol carbonyl-D-glucopyanosyl ester, 2-O-Geraniol carbonyl-D-glucopyanosyl ester or 6-O-Geraniol carbonyl-D-glucopyanosyl ester.
4. the preparation method of a monose Geraniol carbonic acid monoester class compound as claimed in claim 1 is characterized in that, comprises the steps:
In the reaction formula, the protection base of
expression monose;
Steps A): with the Geraniol is starting raw material, and it is dissolved in the suitable solvent, adds alkali and chlorine formylation reagent react, gets chloroformic acid spiceleaf alcohol ester;
Step B): by steps A the chloroformic acid spiceleaf alcohol ester that) obtains is in suitable solvent and under the acid binding agent existence condition; With five carbon monose or six carbon monose direct reaction; Get the mixture of corresponding monose Geraniol carbonic acid monoester class compound and monose Geraniol carbonic acid polyester compounds; Through conventional recrystallization or column chromatography purification, get corresponding monose Geraniol carbonic acid monoester class compound;
Perhaps, adopt following steps to prepare monose Geraniol carbonic acid monoester class compound:
Steps A): with the Geraniol is starting raw material, and it is dissolved in the suitable solvent, adds alkali and chlorine formylation reagent react, gets chloroformic acid spiceleaf alcohol ester;
Step C): by steps A the chloroformic acid spiceleaf alcohol ester that) obtains is in suitable solvent and under the acid binding agent existence condition, and five carbon monose or the reaction of six carbon monose with band protection base get single accordingly Geraniol carbonyl-basic monose carbonats compound of protection;
Step D): by step C the single Geraniol carbonyl that) obtains-basic monose carbonats compound of protection deprotection base under conditions suitable gets corresponding monose Geraniol carbonic acid monoester class compound.
5. the preparation method of monose Geraniol carbonic acid monoester class compound as claimed in claim 4 is characterized in that steps A) in, chlorine formylation reaction solvent for use is selected from: C
3-8Alkanone, C
5-10Fat alkane or naphthenic hydrocarbon, N, dinethylformamide, ether, isopropyl ether, MTBE, THF, glycol dimethyl ether, sherwood oil, C
1-6Lipid acid and C
1-6Ester that Fatty Alcohol(C12-C14 and C12-C18) forms, methylene dichloride, chloroform, 1,2-ethylene dichloride, toluene or acetonitrile are reflected in single solvent or two kinds of mixed solvents and carry out, and the volume ratio of two kinds of mixed solvents is 1: 0.1～10; Chlorine formylation reacts used alkali: basic metal or alkaline earth metal hydroxides, basic metal or alkaline earth metal carbonate, basic metal or alkali metal bicarbonates, piperidines, Pyrrolidine, triethylamine, Tributylamine, trioctylamine, pyridine, N; N-dimethyl--α-Ben Yian, N-methylmorpholine, N-methyl piperidine, triethylene diamine, 1; 8-diazabicyclo [5; 4,0] combination of 11 carbon-7-alkene or above-mentioned various alkali; Used chlorine formylation reagent is: phosgene, superpalite or two (trichloromethyl) carbonic ether; The molar feed ratio of Geraniol, chlorine formylation reagent and alkali is 1.0: 0.2～10.0: 0.5～20.0; Temperature of reaction is-40 ℃～130 ℃; Reaction times is 20 minutes～48 hours.
6. the preparation method of monose Geraniol carbonic acid monoester class compound as claimed in claim 4 is characterized in that step B) in, the reaction solvent for use is selected from: C
3-8Alkanone, C
5-10Fat alkane or naphthenic hydrocarbon, N, dinethylformamide, ether, isopropyl ether, MTBE, THF, glycol dimethyl ether, sherwood oil, C
1-6Lipid acid and C
1-6Ester that Fatty Alcohol(C12-C14 and C12-C18) forms, methylene dichloride, chloroform, 1; 2-ethylene dichloride, toluene, N-Methyl pyrrolidone, DMSO 99.8MIN., water, pyridine or acetonitrile; Be reflected in single solvent or two kinds of mixed solvents and carry out, the volume ratio of two kinds of mixed solvents is 1: 0.1～10; Used acid binding agent is: triethylamine, Tributylamine, trioctylamine, pyridine, N, N-dimethyl--α-Ben Yian, TBAH, basic metal or alkaline earth metal hydroxides, basic metal or alkaline earth metal carbonate or basic metal or alkali metal bicarbonates; The molar feed ratio of five carbon monose or six carbon monose and chloroformic acid spiceleaf alcohol ester is 1.0: 0.2～10.0; The molar feed ratio of acid binding agent and chloroformic acid spiceleaf alcohol ester is 1.0～10.0: 1.0; Temperature of reaction is-40 ℃～90 ℃; Condensation reaction time is 1 hour～48 hours.
7. the preparation method of monose Geraniol carbonic acid monoester class compound as claimed in claim 4 is characterized in that step C) in, the reaction solvent for use is selected from: C
3-8Alkanone, C
5-10Fat alkane or naphthenic hydrocarbon, N, dinethylformamide, ether, isopropyl ether, MTBE, THF, glycol dimethyl ether, sherwood oil, C
1-6Lipid acid and C
1-6Ester that Fatty Alcohol(C12-C14 and C12-C18) forms, methylene dichloride, chloroform, 1; 2-ethylene dichloride, toluene, N-Methyl pyrrolidone, DMSO 99.8MIN., water, pyridine or acetonitrile; Be reflected in single solvent or two kinds of mixed solvents and carry out, the volume ratio of two kinds of mixed solvents is 1: 0.1～10; Used acid binding agent is: triethylamine, Tributylamine, trioctylamine, pyridine, N, N-dimethyl--α-Ben Yian, TBAH, basic metal or alkaline earth metal hydroxides, basic metal or alkaline earth metal carbonate, basic metal or alkali metal bicarbonates; The five carbon monose of band protection base or the molar feed ratio of six carbon monose and chloroformic acid spiceleaf alcohol ester are 1.0: 0.2～10.0; The molar feed ratio of acid binding agent and chloroformic acid spiceleaf alcohol ester is 1.0～10.0: 1.0; Temperature of reaction is-40 ℃～90 ℃; Condensation reaction time is 1 hour～48 hours.
8. the preparation method of monose Geraniol carbonic acid monoester class compound as claimed in claim 4; It is characterized in that; Step D) in, the used acid of deprotection base is: content is that 10%～95% trifluoroacetic acid aqueous solution, content are that 10%～95% aqueous formic acid, content are that 10%～95% acetic acid aqueous solution or content are 1%～37% aqueous hydrochloric acid; The consumption of acid and the ratio of single Geraniol carbonyl-basic monose carbonats compound of protection are: 0.5～50.0: 1.0 (L/mol); Temperature of reaction is-40 ℃～90 ℃; Condensation reaction time is 1 hour～48 hours.
9. the purposes of a monose Geraniol carbonic acid monoester class compound as claimed in claim 1 is as having the application that the humectation performance has the cigarette humectant of flavouring and the effect of slowly-releasing spices concurrently.
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