CN102304154A - Monosaccharide alpha-ionol carbonic acid monoester compounds and preparation method and use thereof - Google Patents
Monosaccharide alpha-ionol carbonic acid monoester compounds and preparation method and use thereof Download PDFInfo
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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
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Abstract
The invention relates to cigarette wetting agent and discloses monosaccharide alpha-ionol carbonic acid monoester compounds and the preparation method of the compounds. The wetting, dampproof and spice sustained release effects of the compounds as cigarette wetting agents are tested. The results of the tests indicate the alpha-ionol carbonic acid monoester compounds have wetting performance for cigarettes and can increase fragrance content, make fragrance released uniformly and improve the visual quality of cigarettes. In a formula, O-R represents five-carbon or six-carbon monosaccharide; and the alpha-ionol carbonyl may at any position in 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 α-ionol 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 is mainly polyhydroxy substances such as Ucar 35, glycerine, sorbyl alcohol at present; 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 is 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 α-ionol carbonic acid monoester class compound.
Second purpose of the present invention is to disclose the preparation method of such monose α-ionol carbonic acid monoester class compound.
The 3rd purpose of the present invention is to disclose such monose α-ionol 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 α-ionol carbonic acid monoester class compound with following general formula:
Wherein, O-R represents the residue of five carbon monose or six carbon monose; α-ionol 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
The preparation method of a kind of aforesaid monose α-ionol carbonic acid monoester class compound is characterized in that available following method preparation:
Reaction formula,
represents a protecting group of monosaccharides;
With α-ionol 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 α-violet alcohol ester; Then in suitable solvent and under the acid binding agent existence condition; Corresponding chloroformic acid α-violet alcohol ester and five carbon monose or six carbon monose direct reaction; Through aftertreatment; Make the mixture of corresponding monose α-ionol carbonic acid monoester class compound and monose α-ionol carbonic acid polyester compounds; Through conventional recrystallization or column chromatography purification, promptly get corresponding monose α-ionol carbonic acid monoester class compound.
Also can with chloroformic acid α-violet alcohol ester of making in suitable solvent with the acid binding agent existence condition under; Five carbon monose or the reaction of six carbon monose with band protection base; The gained list α-basic monose carbonats compound of ionol carbonyl-protection deprotection base under conditions suitable gets corresponding monose α-ionol carbonic acid monoester class compound.
Its concrete preparation method is described below:
Steps A): with α-ionol is starting raw material, and it is dissolved in the suitable solvent, adds alkali and chlorine formylation reagent react, gets chloroformic acid α-violet alcohol ester; Wherein, chlorine formylation reaction solvent for use is selected from: C
3-8Aliphatic ketone, C
5-10Fat alkane or naphthenic hydrocarbon, N, dinethylformamide, ether, isopropyl ether, methyl tertiary butyl ether, tetrahydrofuran (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 α-ionol, 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 α-violet 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 α-ionol carbonic acid monoester class compound and monose α-ionol carbonic acid polyester compounds; Through conventional recrystallization or column chromatography purification, get corresponding monose α-ionol carbonic acid monoester class compound;
Wherein, the reaction solvent for use is selected from: C
3-8Aliphatic ketone, C
5-10Fat alkane or naphthenic hydrocarbon, N, dinethylformamide, ether, isopropyl ether, methyl tertiary butyl ether, tetrahydrofuran (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, dimethyl sulfoxide (DMSO), water, pyridine 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; Preferred solvent is: tetrahydrofuran (THF), N, dinethylformamide, methylene dichloride, ethyl 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 α-violet 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 α-violet 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 α-violet alcohol ester that obtains in suitable solvent with the acid binding agent existence condition under; Five carbon monose or the reaction of six carbon monose with band protection base get single accordingly α-basic monose carbonats compound of ionol carbonyl-protection;
Wherein, the reaction solvent for use is selected from: C
3-8Aliphatic ketone, C
5-10Fat alkane or naphthenic hydrocarbon, N, dinethylformamide, ether, isopropyl ether, methyl tertiary butyl ether, tetrahydrofuran (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, dimethyl sulfoxide (DMSO), water, pyridine 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; Preferred solvent is: tetrahydrofuran (THF), N, dinethylformamide, methylene dichloride, ethyl 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 α-violet 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 α-violet 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 single α that the obtains-basic monose carbonats compound of ionol carbonyl-protection deprotection base under conditions suitable) gets corresponding monose α-ionol 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 or 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 single α-ionol carbonyl-basic monose carbonats compound of protection 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 α of the present invention-ionol 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 α of the present invention-ionol 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 α of the present invention-ionol 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 disclosed monose α of the present invention-fragrance of ionol 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 α-ionol 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; Product toxicological harmless after the disclosed monose α of the present invention-ionol carbonic acid monoesters class cigarette humectant burning; Safe in utilization, more help the security of sucking of tobacco, be easy to apply.
Embodiment
Can further describe the present invention through the following examples, 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-α-violet alcohol ester synthetic
In reaction flask, add 2000ml CH
2Cl
2With two (trichloromethyl) carbonic ether 129g (0.44mol), after stirring at room to solid dissolves entirely, reaction flask is put in the cryosel bath; After being cooled to-10 ℃, add α-ionol 1.28mol, fully after the dissolving; Drip the 200ml pyridine, the control rate of addition makes reacting liquid temperature maintain 0～5 ℃; Drip and finish; Reaction solution is warming up to room temperature naturally, and stirring reaction spends the night, and promptly gets the dichloromethane solution of chloroformic acid-α-violet alcohol ester; Need not purifying and promptly can be used for step reaction down, quantitative yield.
Embodiment 2: chloroformic acid-α-violet 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-α-violet alcohol ester, need not purifying and promptly can be used for step reaction down, quantitative yield.
The preparation of embodiment 3:3-O-α-ionol carbonyl-D-glucopyanosyl ester (compound I)
Get chloroformic acid-α-violet alcohol ester dichloromethane solution 0.048mol that embodiment 1 makes; Be added dropwise to be cooled to-5～0 ℃ 1; 2:5; In 6-two-O-isopropylidene-D-grape furanose 0.04mol, triethylamine 0.07mol and the methylene dichloride 85ml mixed solution; Stirring at room reaction 24h; Reaction changes reaction solution in the separating funnel over to after finishing, and organic layer is used 5%HCl aqueous solution 20ml, saturated NaHCO successively
3Aqueous solution 20ml and saturated NaCl aqueous solution 20ml washing are through anhydrous Na
2SO
4Dry; Filter, remove solvent under reduced pressure, add 70% trifluoroacetic acid aqueous solution 45ml in the resistates; 15～25 ℃ of stirring reaction 2h; Remove solvent under reduced pressure, gained 3-O-α-ionol carbonyl-D-glucopyanosyl ester crude product through purification by silica gel column chromatography (elutriant: chloroform/methanol=25/1, v/v); Collect the product component; Remove solvent under reduced pressure, get 3-O-α-ionol carbonyl-D-glucopyanosyl ester white foam body, yield 60.0%; HR-TOFMS (+Q) m/z:423.1991 ([C
20H
32O
8+ Na]
+Calculated value: 423.1995).
The preparation of embodiment 4:6-O-α-ionol carbonyl-D-gala pyrans sugar ester (compound I I)
Operating process is with embodiment 3; Just with 1; 2:5; 6-two-O-isopropylidene-D-grape furanose is with 1,2:3, and 4-two-O-isopropylidene-D-gala pyranose substitutes; Triethylamine substitutes with pyridine; 70% trifluoroacetic acid aqueous solution substitutes with 80% aqueous formic acid, gets 6-O-α-ionol carbonyl-D-gala pyrans sugar ester white foam body, yield 81.0%; HR-TOFMS (+Q) m/z:423.1993 ([C
20H
32O
8+ Na]
+Calculated value: 423.1995).
The preparation of embodiment 5:2-O-α-ionol carbonyl-D-gala pyrans sugar ester (compound III) and 3-O-α-ionol carbonyl-D-gala pyrans sugar ester (compound IV)
The compound III compound IV
Operating process is with embodiment 3; Just with 1; 2:5,6-two-O-isopropylidene-D-grape furanose are with 4, and 6-O-isopropylidene-D-semi-lactosi methyl glucoside substitutes; 70% trifluoroacetic acid aqueous solution substitutes with 20% aqueous hydrochloric acid; (elutriant: chloroform/methanol=25/1 v/v), gets 2-O-α-ionol carbonyl-D-gala pyrans sugar ester to crude product through purification by silica gel column chromatography; Yield 27.0%, HR-TOFMS (+Q) m/z:423.2000 ([C
20H
32O
8+ Na]
+Calculated value: 423.1995); Obtain 3-O-α-ionol carbonyl-D-gala pyrans sugar ester simultaneously, yield 22.0%, HR-TOFMS (+Q) m/z:423.1990 ([C
20H
32O
8+ Na]
+Calculated value: 423.1995).
The preparation of embodiment 6:4-O-α-ionol carbonyl-D-mannopyranose ester (compound V) and 6-O-α-ionol carbonyl-D-mannopyranose ester (compound VI)
Compound V compound VI
Operating process is with embodiment 3; Just with 1; 2:5,6-two-O-isopropylidene-D-grape furanose are with 2, and 3-O-isopropylidene-D-seminose methyl glucoside substitutes; 70% trifluoroacetic acid aqueous solution substitutes with 20% aqueous hydrochloric acid; (elutriant: chloroform/methanol=25/1 v/v), gets 4-O-α-ionol carbonyl-D-mannopyranose ester to crude product through purification by silica gel column chromatography; Yield 12.0%, HR-TOFMS (+Q) m/z:423.1998 ([C
20H
32O
8+ Na]
+Calculated value: 423.1995); Obtain 6-O-α-ionol carbonyl-D-mannopyranose ester simultaneously, yield 60.0%, HR-TOFMS (+Q) m/z:423.1994 ([C
20H
32O
8+ Na]
+Calculated value: 423.1995).
The preparation of embodiment 7:2-O-α-ionol carbonyl-D-mannopyranose ester (compound VI I) and 3-O-α-ionol carbonyl-D-mannopyranose ester (compound VIII)
Compound VI I compound VIII
Operating process is with embodiment 3; Just with 1; 2:5,6-two-O-isopropylidene-D-grape furanose are with 4, and 6-O-isopropylidene-D-seminose methyl glucoside substitutes; 70% trifluoroacetic acid aqueous solution substitutes with 20% aqueous hydrochloric acid; (elutriant: chloroform/methanol=25/1 v/v), gets 2-O-α-ionol carbonyl-D-mannopyranose ester to crude product through purification by silica gel column chromatography; Yield 35.0%, HR-TOFMS (+Q) m/z:423.1992 ([C
20H
32O
8+ Na]
+Calculated value: 423.1995); Obtain 3-O-α-ionol carbonyl-D-mannopyranose ester simultaneously, yield 31.0%, HR-TOFMS (+Q) m/z:423.2003 ([C
20H
32O
8+ Na]
+Calculated value: 423.1995).
The preparation of embodiment 8:1-O-α-ionol 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-α-ionol carbonyl-D-fruit pyrans sugar ester white foam body, yield 64.0%; HR-TOFMS (+Q) m/z:423.1995 ([C
20H
32O
8+ Na]
+Calculated value: 423.1995).
The preparation of embodiment 9:3-O-α-ionol 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-α-ionol carbonyl-D-fruit pyrans sugar ester white foam body, yield 66.0%; HR-TOFMS (+Q) m/z:423.1996 ([C
20H
32O
8+ Na]
+Calculated value: 423.1995).
The preparation of embodiment 10:1-O-α-ionol carbonyl-D-sorb pyrans sugar ester (compounds X I)
Get chloroformic acid α-violet 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
4Dry; Filter; Remove solvent under reduced pressure; Gained 1-O-α-ionol carbonyl-D-sorb pyrans sugar ester crude product is through purification by silica gel column chromatography (elutriant: chloroform/methanol=25/1; V/v), collect the product component, remove solvent under reduced pressure; Get 1-O-α-ionol carbonyl-D-sorb pyrans sugar ester white foam body, yield 52.0%; HR-TOFMS (+Q) m/z:423.1998 ([C
20H
32O
8+ Na]
+Calculated value: 423.1995).
The preparation of the ancient Lip river pyrans sugar ester of embodiment 11:6-O-α-ionol 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-α-ionol carbonyl-D-pyrans sugar ester white foam body, yield 20.0%; HR-TOFMS (+Q) m/z:423.1992 ([C
20H
32O
8+ Na]
+Calculated value: 423.1995).
The preparation of embodiment 12:1-O-α-ionol carbonyl-Nitranitol (compounds X III)
Operating process just substitutes the D-sorbose with embodiment 10 with N.F,USP MANNITOL, get 1-O-α-ionol carbonyl-Nitranitol white foam body, yield 46.0%; HR-TOFMS (+Q) m/z:425.2157 ([C
20H
34O
8+ Na]
+Calculated value: 425.2151).
The preparation of embodiment 13:1-O-α-ionol carbonyl-sorbitol ester (compounds X IV)
Operating process just substitutes the D-sorbose with embodiment 10 with sorbyl alcohol, get 1-O-α-ionol carbonyl-sorbitol ester white foam body, yield 40.0%; HR-TOFMS (+Q) m/z:425.2150 ([C
20H
34O
8+ Na]
+Calculated value: 425.2151).
The preparation of embodiment 14:5-O-α-ionol 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-α-ionol carbonyl-D-wood furans sugar ester white foam body, yield 60.0%; HR-TOFMS (+Q) m/z:393.1893 ([C
19H
30O
7+ Na]
+Calculated value: 393.1889).
Embodiment 15:6-O-α-ionol 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-α-ionol carbonyl-1,4-sorbitan ester white foam body, yield 70.0%; HR-TOFMS (+Q) m/z:407.2045 ([C
20H
32O
7+ Na]
+Calculated value: 407.2046).
Embodiment 16:1-O-α-ionol 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-α-ionol carbonyl-3,6-sorbitan ester white foam body, yield 67.0%; HR-TOFMS (+Q) m/z:407.2041 ([C
20H
32O
7+ Na]
+Calculated value: 407.2046).
The preparation of embodiment 17:5-O-α-ionol 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-α-ionol carbonyl-D-nuclear furans sugar ester white foam body, yield 47.0%; HR-TOFMS (+Q) m/z:393.1892 ([C
19H
30O
7+ Na]
+Calculated value: 393.1889).
The preparation of embodiment 18:5-O-α-ionol carbonyl-D-arbinofuranose ester (compounds X IX)
Operating process just substitutes the D-sorbose with embodiment 10 with the D-pectinose, get 5-O-α-ionol carbonyl-D-arbinofuranose ester white foam body, yield 41.0%; HR-TOFMS (+Q) m/z:393.1885 ([C
19H
30O
7+ Na]
+Calculated value: 393.1889).
The preparation of embodiment 19:5-O-α-ionol 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-α-ionol carbonyl-D-lysol furans sugar ester white foam body, yield 54.0%; HR-TOFMS (+Q) m/z:393.1883 ([C
19H
30O
7+ Na]
+Calculated value: 393.1889).
The preparation of embodiment 20:1-O-α-ionol carbonyl-D-ribulose ester (compounds X XI)
Operating process just substitutes the D-sorbose with embodiment 10 with the D-ribulose, get 1-O-α-ionol carbonyl-D-ribulose ester white foam body, yield 33.0%; HR-TOFMS (+Q) m/z:393.1888 ([C
19H
30O
7+ Na]
+Calculated value: 393.1889).
The preparation of embodiment 21:1-O-α-ionol carbonyl-D-xylulose ester (compounds X XII)
Operating process just substitutes the D-sorbose with embodiment 10 with the D-xylulose, get 1-O-α-ionol carbonyl-D-xylulose ester white foam body, yield 46.0%; HR-TOFMS (+Q) m/z:393.1887 ([C
19H
30O
7+ Na]
+Calculated value: 393.1889).
The preparation of embodiment 22:1-O-α-ionol carbonyl-D-glucopyanosyl ester (compounds X XIII), 2-O-α-ionol carbonyl-D-glucopyanosyl ester (compounds X XIV) and 6-O-α-ionol 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-α-ionol carbonyl-D-glucopyanosyl ester white foam body, and yield 15.0%, HR-TOFMS (+Q) m/z:423.1988 ([C
20H
32O
8+ Na]
+Calculated value: 423.1995); Obtain 2-O-α-ionol carbonyl-D-glucopyanosyl ester white foam body simultaneously, yield 12.0%, HR-TOFMS (+Q) m/z:423.1996 ([C
20H
32O
8+ Na]
+Calculated value: 423.1995); Also obtain 6-O-α-ionol carbonyl-D-glucopyanosyl ester white foam body simultaneously, yield 54.0%; HR-TOFMS (+Q) m/z:423.1997 ([C
20H
32O
8+ Na]
+Calculated value: 423.1995).
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 α-ionol carbonic acid monoester class compound (I～XXV) the humectation effect of pipe tobacco has been carried out the experiment contrast.Aqueous ethanolic solution with 50% is a solvent, above-claimed cpd and Ucar 35 is mixed with solution and evenly sprays 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 monose α-ionol 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 α-ionol carbonic acid monoester class compound 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 α-ionol carbonic acid monoester class compound (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 α-ionol carbonic acid monoester class compound 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 α-ionol carbonic acid monoester class compound.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 Gas Chromatography-mass Spectrometer (GCMS) by helium and carries out qualitative analysis.
Mensuration result shows; These compounds all have aroma component such as α-ionol to produce at 200 ℃, 450 ℃ and 700 ℃, show that disclosed five carbon of the present invention or six carbon monose α-ionol carbonic acid monoester class compound 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 α-ionol 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 be 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 α-ionol carbonic acid monoester class compound have increases perfume quantity, releases the fragrant all even effect that improves the cigarette aesthetic quality.
Claims (9)
1. one type of monose α-ionol 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; α-ionol carbonyl is positioned at any possible position of five carbon or six carbon monose.
2. monose α as claimed in claim 1-ionol carbonic acid monoester class compound; 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, the 6-anhydrous sorbitol.
3. monose α as claimed in claim 1 or 2-ionol carbonic acid monoester class compound; It is characterized in that; Said compound is selected from: 3-O- α-ionol carbonyl-D- glucopyanosyl ester; 6-O- α-ionol carbonyl-D- gala pyrans sugar ester; 2-O- α-ionol carbonyl-D- gala pyrans sugar ester; 3-O- α-ionol carbonyl-D- gala pyrans sugar ester; 4-O- α-ionol carbonyl-D- mannopyranose ester; 6-O- α-ionol carbonyl-D- mannopyranose ester; 2-O- α-ionol carbonyl-D- mannopyranose ester; 3-O- α-ionol carbonyl-D- mannopyranose ester; 1-O- α-ionol carbonyl-D- fruit pyrans sugar ester; 3-O- α-ionol carbonyl-D- fruit pyrans sugar ester; 1-O- α-ionol carbonyl-D- sorb pyrans sugar ester; The ancient Lip river of 6-O- α-ionol carbonyl-D- pyrans sugar ester; 1-O- α-ionol carbonyl-Nitranitol; 1-O- α-ionol carbonyl-sorbitol ester; 5-O- α-ionol carbonyl-D- wood furans sugar ester; 6-O- α-ionol carbonyl-1; The 4- sorbitan ester; 1-O- α-ionol carbonyl-3; The 6- sorbitan ester; 5-O- α-ionol carbonyl-D- nuclear furans sugar ester; 5-O- α-ionol carbonyl-D- arabinofuranose ester; 5-O- α-ionol carbonyl-D- lysol furans sugar ester; 1-O- α-ionol carbonyl-D- ribulose ester; 1-O- α-ionol carbonyl-D- xylulose ester; 1-O- α-ionol carbonyl-D- glucopyanosyl ester, 2-O- α-ionol carbonyl-D- glucopyanosyl ester or 6-O- α-ionol carbonyl-D- glucopyanosyl ester.
4. the preparation method of monose α as claimed in claim 1-ionol carbonic acid monoester class compound is characterized in that comprising the steps:
Reaction formula,
represents monosaccharide protecting group;
Steps A): with α-ionol is starting raw material, and it is dissolved in the suitable solvent, adds alkali and chlorine formylation reagent react, gets chloroformic acid α-violet alcohol ester;
Step B): by steps A the chloroformic acid α-violet 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 α-ionol carbonic acid monoester class compound and monose α-ionol carbonic acid polyester compounds; Through conventional recrystallization or column chromatography purification, get corresponding monose α-ionol carbonic acid monoester class compound;
Also available following steps prepare monose α-ionol carbonic acid monoester class compound:
Steps A): with α-ionol is starting raw material, and it is dissolved in the suitable solvent, adds alkali and chlorine formylation reagent react, gets chloroformic acid α-violet alcohol ester;
Step C): by steps A the chloroformic acid α-violet 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 α-basic monose carbonats compound of ionol carbonyl-protection;
Step D): by step C the single α that the obtains-basic monose carbonats compound of ionol carbonyl-protection deprotection base under conditions suitable) gets corresponding monose α-ionol carbonic acid monoester class compound.
5. the preparation method of monose α as claimed in claim 4-ionol carbonic acid monoester class compound is characterized in that steps A) in, chlorine formylation reaction solvent for use is selected from: C
3-8Aliphatic ketone, C
5-10Fat alkane or naphthenic hydrocarbon, N, dinethylformamide, ether, isopropyl ether, methyl tertiary butyl ether, tetrahydrofuran (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, two (trichloromethyl) carbonic ether; The molar feed ratio of α-ionol, 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 α as claimed in claim 4-ionol carbonats compound is characterized in that step B) in, the reaction solvent for use is selected from: C
3-8Aliphatic ketone, C
5-10Fat alkane or naphthenic hydrocarbon, N, dinethylformamide, ether, isopropyl ether, methyl tertiary butyl ether, tetrahydrofuran (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, dimethyl sulfoxide (DMSO), 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 molar feed ratio of five carbon monose or six carbon monose and chloroformic acid α-violet alcohol ester is 1.0: 0.2～10.0; The molar feed ratio of acid binding agent and chloroformic acid α-violet 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 α as claimed in claim 4-ionol carbonats compound is characterized in that step C) in, the reaction solvent for use is selected from: C
3-8Aliphatic ketone, C
5-10Fat alkane or naphthenic hydrocarbon, N, dinethylformamide, ether, isopropyl ether, methyl tertiary butyl ether, tetrahydrofuran (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, dimethyl sulfoxide (DMSO), 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 α-violet alcohol ester are 1.0: 0.2～10.0; The molar feed ratio of acid binding agent and chloroformic acid α-violet 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 α as claimed in claim 4-ionol carbonats compound; 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 α-ionol 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 monose α as claimed in claim 1-ionol carbonats compound 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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