CN102311465B - 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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- CN102311465B CN102311465B CN201110260085.3A CN201110260085A CN102311465B CN 102311465 B CN102311465 B CN 102311465B CN 201110260085 A CN201110260085 A CN 201110260085A CN 102311465 B CN102311465 B CN 102311465B
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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 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 a class monose ester cigarette humectant, be specifically related to monose Geraniol carbonic acid monoester class compound, its preparation method and conduct thereof and there is the application that humid keeping 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 of < < tobacco industry (2006-2020) > > explicitly point out, and flavouring humectation technical study is one of main direction of industry science and technology coming years research and scientific and technical innovation.
Desirable humectant should have physics humectation and sense organ humectation function concurrently.Physics humectation is moisturizing, refer to maintain pipe tobacco in the course of processing water ratio, improve the resistance to processibility of pipe tobacco and maintain the water ratio of finished cigarettes; Sense organ humectation refers to and improves smoking property of cigarette comfort level, as reduced flue gas drying sense and pungency, improving pleasant impression etc.The humectant adopting in China's production of cigarettes is at present mainly the polyhydroxy substances such as propylene glycol, glycerine, sorbyl alcohol, but it maintains finished cigarettes water ratio and improves that to suck the effect of comfort level really not satisfactory, as in relative humidity hour, there is the 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 larger, 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 and even goes mouldy.
Desirable sweetener should possess stable in properties, release the features such as perfume is even, high safety.The sweetener major part that at present perfuming cigarette is used is the compound that molecular weight is lower, boiling point is low, volatility is stronger, exists in high temperature process process easily volatilely between loss, shelf lives to release the fragrant disadvantage such as inhomogeneous while losing fragrance, suction.
Therefore, research and development have the novel humectant that better humid keeping performance has flavouring and the effect of slowly-releasing spices concurrently, to improving humid keeping performance and the international competitiveness of China's cigarette product, have 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 object of the present invention is to disclose the preparation method of such monose Geraniol carbonic acid monoester class compound.
The 3rd object of the present invention is to disclose such monose Geraniol carbonic acid monoester class compound as the purposes that has humid keeping performance and have concurrently the new cigarette humectant of flavouring and the effect of slowly-releasing spices.
The object of the present invention is achieved 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; 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 3,6-anhydrous sorbitol.
Second object of the present invention is achieved in that
A preparation method for monose Geraniol carbonic acid monoester class compound as above, can prepare with the following method:
In reaction formula,
the protecting group that represents monose;
Take Geraniol as starting raw material, be dissolved in suitable solvent, add alkali and chlorine formylation reagent, after reaction for some time, through aftertreatment, make chloroformic acid spiceleaf alcohol ester; Then in suitable solvent and under 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, through conventional recrystallization or column chromatography purification, obtain corresponding monose Geraniol carbonic acid monoester class compound.
Also can be by the chloroformic acid spiceleaf alcohol ester making in suitable solvent and under acid binding agent existence condition; react with five carbon monose or six carbon monose with protecting group; gained Geraniol carbonyl-protecting group monose carbonic acid monoester class compound Deprotection under conditions suitable, obtains corresponding monose Geraniol carbonic acid monoester class compound.
Its concrete preparation method is described below:
Steps A): take Geraniol as starting raw material, be dissolved in suitable solvent, add alkali and chlorine formylation reagent react, obtain chloroformic acid spiceleaf alcohol ester; Wherein, Chloroformylation solvent for use is selected from: C
3-8aliphatic ketone, C
5-10fat alkane or naphthenic hydrocarbon, DMF, 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 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;
Chloroformylation alkali used is: 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-phenylethylamine, 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 bicarbonate, triethylamine or pyridine;
Chlorine formylation reagent used 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 preferably 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) obtaining is in suitable solvent and under acid binding agent existence condition, with five carbon monose or six carbon monose direct reaction, obtain 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, obtain corresponding monose Geraniol carbonic acid monoester class compound;
Wherein, reaction solvent for use is selected from: C
3-8aliphatic ketone, C
5-10fat alkane or naphthenic hydrocarbon, DMF, 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 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), DMF, methylene dichloride, ethyl acetate or pyridine;
Acid binding agent used is: triethylamine, Tributylamine, trioctylamine, pyridine, N, N-dimethyl-α-phenylethylamine, TBAH, basic metal or alkaline earth metal hydroxides, basic metal or alkaline earth metal carbonate, basic metal or alkali metal bicarbonates, preferably acid binding agent is: triethylamine, pyridine or sodium bicarbonate;
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 preferably 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 preferably 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 by by steps A the chloroformic acid spiceleaf alcohol ester) obtaining, in suitable solvent and under acid binding agent existence condition, reacts with five carbon monose or six carbon monose with protecting group, obtains corresponding Geraniol carbonyl-protecting group monose carbonic acid monoester class compound;
Wherein, reaction solvent for use is selected from: C
3-8aliphatic ketone, C
5-10fat alkane or naphthenic hydrocarbon, DMF, 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 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), DMF, methylene dichloride, ethyl acetate or pyridine;
Acid binding agent used is: triethylamine, Tributylamine, trioctylamine, pyridine, N, N-dimethyl-α-phenylethylamine, TBAH, basic metal or alkaline earth metal hydroxides, basic metal or alkaline earth metal carbonate, basic metal or alkali metal bicarbonates, preferably acid binding agent is: triethylamine, pyridine or sodium bicarbonate;
With five carbon monose of protecting group or the molar feed ratio of six carbon monose and chloroformic acid spiceleaf alcohol ester, be 1.0: 0.2～10.0, preferably 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 preferably 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-protecting group monose carbonic acid monoester class compound Deprotection under conditions suitable) obtaining, obtains corresponding monose Geraniol carbonic acid monoester class compound; Wherein, Deprotection acid used is: the aqueous hydrochloric acid that the acetic acid aqueous solution that the aqueous formic acid that the trifluoroacetic acid aqueous solution that content is 10%～95%, content are 10%～95%, content are 10%～95% or content are 1%～37%, and preferred acid is: the aqueous hydrochloric acid that the acetic acid aqueous solution that the aqueous formic acid that the trifluoroacetic acid aqueous solution that content is 50%～90%, content are 50%～95%, content are 50%～95% or content are 10%～37%; The consumption of acid and the ratio of Geraniol carbonyl-protecting group monose carbonic acid monoester class compound are: 0.5～50.0: 1.0 (L/mol), and preferably 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 object of the present invention is achieved in that
Monose Geraniol carbonic acid monoester class compound disclosed in this invention can be used as cigarette humectant; this compounds has certain water-soluble and fat-soluble; for non-ionic type glycosyl surfactant active; can stablize cigarette water ratio by the bilayer protective membrane of being separated by tobacco surface formation profit, reach the effect of humectation, protection against the tide, slowly-releasing spices and flavouring.
Compared with prior art, beneficial effect of the present invention is as follows:
1, monose Geraniol carbonic acid monoesters class cigarette humectant disclosed in this invention can have humectation and moistureproof two kinds of effects by the bilayer protective membrane of being separated by tobacco surface formation profit simultaneously; the speed that the tobacco of processing through this class humectant dries out in dry climatope is slow; and the speed that absorbs moisture in moist climatope is also slow, can effectively slow down tobacco moisture with the variation of envrionment conditions.
2, monose Geraniol carbonic acid monoesters class cigarette humectant disclosed in this invention also can be by the profit forming on tobacco surface be separated by bilayer protective membrane and the volatilization of flavour ingredient in significantly slowing down tobacco, thereby has certain slowly-releasing spices effect.
3, the fragrance of monose Geraniol carbonic acid monoesters class cigarette humectant disclosed in this invention own is less or there is no fragrance, but can hot crackedly discharge feature aroma component in result of combustion of tobacco process, makes the more comfortable harmony of fragrance of cigarette.Saccharide compound itself is present in tobacco, and Geraniol is widely used in actual production as cigarette deodorant tune, and therefore, this class cigarette humectant disclosed in this invention and tobacco have good compatibleness, safe.
4, compare with widely used propylene glycol in current tobacco industry or glycerine, the product toxicological harmless after monose Geraniol carbonic acid monoesters class cigarette humectant burning disclosed in this invention, is used safety, is more conducive to the security of sucking of tobacco, is easy to apply.
Embodiment
By the following examples, can conduct further description the present invention, yet scope of the present invention is not limited to following embodiment.One of skill in the art can understand, and is not deviating under the prerequisite of 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), stirring at room to solid complete molten after, reaction flask is put during cryosel bathes, be cooled to after-10 ℃, add Geraniol 1.28mol, after dissolving completely, drip 200ml pyridine, control rate of addition, make 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 obtains the dichloromethane solution of chloroformic acid spiceleaf alcohol ester, without purifying, can be used for the next step, quantitative yield.
Embodiment 2: chloroformic acid spiceleaf alcohol ester synthetic
Operating process, with embodiment 1, just substitutes two (trichloromethyl) carbonic ethers with superpalite, pyridine substitutes with sodium bicarbonate, CH
2cl
2with toluene, substitute, obtain the toluene solution of chloroformic acid spiceleaf alcohol ester, without purifying, can be used for the next step, 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, in 6-bis--O-isopropylidene-D-grape furanose 0.05mol, triethylamine 0.08mol and methylene dichloride 100ml mixed solution, stirring at room reaction 20h, after reaction finishes, reaction solution is proceeded in separating funnel, organic layer is used 5%HCl aqueous solution 25ml, saturated NaHCO successively
3aqueous solution 25ml and saturated NaCl aqueous solution 25ml washing, through anhydrous Na
2sO
4dry, filter, remove solvent under reduced pressure, in resistates, add 70% trifluoroacetic acid aqueous solution 50ml, 15～25 ℃ of stirring reaction 3h, remove solvent under reduced pressure, gained 3-O-Geraniol carbonyl-D-glucopyanosyl ester crude product through purification by silica gel column chromatography (elutriant: chloroform: methyl alcohol=20: 1, v/v), collect product component, remove solvent under reduced pressure, obtain 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 embodiment 3, just by 1,2:5,6-bis--O-isopropylidene-D-grape 1,2:3 for furanose, 4-bis--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, obtain 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)
Compound III compound IV
Operating process is with embodiment 3, just by 1,2:5,6-bis--O-isopropylidene-D-grape furanose substitutes with 4,6-O-isopropylidene-D-semi-lactosi methyl glucoside, 70% trifluoroacetic acid aqueous solution substitutes with 20% aqueous hydrochloric acid, crude product is through purification by silica gel column chromatography (elutriant: chloroform/methanol=10/1, v/v), obtains 2-O-Geraniol carbonyl-D-gala pyrans sugar ester, 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, yield 32.0%, HR-TOFMS (+Q) m/z:383.1679 ([C simultaneously
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 embodiment 3, just by 1,2:5,6-bis--O-isopropylidene-D-grape furanose substitutes with 2,3-O-isopropylidene-D-MANNOSE methyl glucoside, 70% trifluoroacetic acid aqueous solution substitutes with 20% aqueous hydrochloric acid, crude product is through purification by silica gel column chromatography (elutriant: chloroform/methanol=10/1, v/v), obtains 4-O-Geraniol carbonyl-D-mannopyranose ester, 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, yield 53.0%, HR-TOFMS (+Q) m/z:383.1680 ([C simultaneously
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 VI II)
Compound VI I compound VI II
Operating process is with embodiment 3, just by 1,2:5,6-bis--O-isopropylidene-D-grape furanose substitutes with 4,6-O-isopropylidene-D-MANNOSE methyl glucoside, 70% trifluoroacetic acid aqueous solution substitutes with 20% aqueous hydrochloric acid, crude product is through purification by silica gel column chromatography (elutriant: chloroform/methanol=10/1, v/v), obtains 2-O-Geraniol carbonyl-D-mannopyranose ester, 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, yield 36.0%, HR-TOFMS (+Q) m/z:383.1685 ([C simultaneously
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, with embodiment 3, is by 1,2:5,6-bis--O-isopropylidene-D-grape 2,3:4 for furanose, and 5-bis--O-isopropylidene-D-fruit pyranose substitutes, and obtains 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, with embodiment 3, is by 1,2:5,6-bis--O-isopropylidene-D-grape 1,2:4 for furanose, and 5-bis--O-isopropylidene-D-fruit pyranose substitutes, and obtains 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 D-sorbose 0.05mol, the pyridine 0.08mol and the N that are cooled to-5～0 ℃, in 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 to 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, through anhydrous Na
2sO
4dry, filter, remove solvent under reduced pressure, gained 1-O-Geraniol carbonyl-D-sorb pyrans sugar ester crude product is through purification by silica gel column chromatography (elutriant: chloroform/methanol=10/1, v/v), collect product component, remove solvent under reduced pressure, obtain 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, with embodiment 10, just substitutes D-sorbose with D-gulose, obtain 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, with embodiment 10, just substitutes D-sorbose with N.F,USP MANNITOL, obtain 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, with embodiment 10, just substitutes D-sorbose with sorbyl alcohol, obtain 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 by 1,2:5,6-bis--O-isopropylidene-D-grape 1,2-O-isopropylidene for furanose-D-wood furanose substitutes, and obtains 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).
The preparation of embodiment 15:6-O-Geraniol carbonyl-Isosorbide-5-Nitrae-sorbitan ester (compounds X VI)
Operating process, with embodiment 10, just substitutes D-sorbose with Isosorbide-5-Nitrae-anhydrous sorbitol, obtain 6-O-Geraniol carbonyl-Isosorbide-5-Nitrae-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, with embodiment 10, just substitutes D-sorbose with 3,6-anhydrous sorbitol, obtain 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-core furans sugar ester (compounds X VIII)
Operating process, with embodiment 10, just substitutes D-sorbose with D-ribose, obtain 5-O-Geraniol carbonyl-D-core 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, with embodiment 10, just substitutes D-sorbose with D-R, obtain 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, with embodiment 10, just substitutes D-sorbose with D-lyxose, obtain 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, with embodiment 10, just substitutes D-sorbose with D-ribulose, obtain 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, with embodiment 10, just substitutes D-sorbose with D-xylulose, obtain 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, with embodiment 10, just substitutes D-sorbose with D-Glucose, obtain 1-O-Geraniol carbonyl-D-glucopyanosyl ester white foam body, 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, yield 10.0%, HR-TOFMS (+Q) m/z:383.1676 ([C simultaneously
17h
28o
8+ Na]
+calculated value: 383.1682); Also obtain 6-O-Geraniol carbonyl-D-glucopyanosyl ester white foam body, yield 52.0%, HR-TOFMS (+Q) m/z:383.1680 ([C simultaneously
17h
28o
8+ Na]
+calculated value: 383.1682).
Embodiment 23: humectation and moisture-proof role test
The blank pipe tobacco of take is contrast with adding the pipe tobacco of propylene glycol, and above-mentioned five carbon or six carbon monose Geraniol carbonic acid monoester class compounds (I～XXV) have been carried out to experiment contrast to the humectation effect of pipe tobacco.50% the aqueous ethanolic solution of take is solvent, above-claimed cpd and propylene glycol is mixed with to solution and evenly sprays into respectively in blank pipe tobacco (addition be pipe tobacco weight 0.4%), sprays into the solvent of equivalent in blank pipe tobacco.Each tobacco sample after application of sample is placed in after 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 Duplicate Samples are wherein positioned in the encloses container of 22 ℃ of relative humidity 45%, temperature, another two parts of Duplicate Samples are positioned in the encloses container of 22 ℃ of relative humidity 85%, temperature; Every 24h weighs 1 time, the water ratio when calculating each part of pipe tobacco and measure according to the weight differential with initial weight and initial aqueous rate; Measurement result is got the average of 2 Duplicate Samples, and makes the time dependent curve of water ratio; Measure and to continue to the dehydration of each part of pipe tobacco or water suction always and reach in a basic balancely, the results are shown in Table 1 (" RH " representative " relative humidity " in 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 in various degree higher than propylene glycol contrast pipe tobacco or blank pipe tobacco, and under the condition of 22 ℃ of relative humidity 85%, temperature, the equilibrium moisture content of above-mentioned monose ester compound lower than propylene glycol contrast pipe tobacco or blank pipe tobacco, shows that five carbon disclosed in this invention or six carbon monose Geraniol carbonic acid monoester class compounds have good humectation and moisture-proof role to pipe tobacco in various degree.
Embodiment 24: slowly-releasing spices effect test
Take that to add the tobacco sample of propylene glycol be contrast, above-mentioned five carbon or six carbon monose Geraniol carbonic acid monoester class compounds (I～XXV) have been carried out to experiment contrast to the slowly-releasing spices effect of pipe tobacco.Above-mentioned monose ester compound solution and propylene glycol solution sprayed into respectively in pipe tobacco to (addition be pipe tobacco weight 0.4%) and place after certain hour, sampling respectively 0.5 gram, the methylene dichloride of take carries out supersound extraction as solvent; Dichloromethane solution after extraction, after filtering with microporous membrane, utilizes gas chromatograph-mass spectrometer to analyze the content of flavor matter in filtrate.
Test result shows, the tobacco sample that in the tobacco sample of processing through above-mentioned monose ester compound, the content of typical flavor matter was all processed higher than propylene glycol in various degree, shows that five carbon disclosed in this invention or six carbon monose Geraniol carbonic acid monoester class compounds have certain effect that slows down flavour ingredient volatilization in pipe tobacco.
Embodiment 25: thermo-cracking composition is analyzed
Adopt online thermal cracking-gas chromatograph-mass spectrometric hyphenated technique, being thermally cracked to of above-mentioned five carbon or six carbon monose Geraniol carbonic acid monoester class compounds (I～XXV) minute is studied.Take respectively about 0.2mg sample, be placed in solid sampler, carry out moment cracking at 200 ℃, 450 ℃ and 700 ℃, cracking atmosphere is helium, and split product is directly imported in Gas Chromatography-mass Spectrometer (GCMS) and carried out qualitative analysis by helium.
Measurement result demonstration, these compounds all have the aroma components such as Geraniol to produce at 200 ℃, 450 ℃ and 700 ℃, show that five carbon disclosed in this invention or six carbon monose Geraniol carbonic acid monoester class compounds have the effect that thermo-cracking discharges aroma component.
Embodiment 26: sensory evaluating smoking evaluates
For five carbon disclosed in this invention or six carbon monose Geraniol carbonic acid monoester class compounds (I～XXV), carried out with the following method sensory evaluating smoking's evaluation.
50% the aqueous ethanolic solution of take is solvent, above-claimed cpd and propylene glycol are mixed with to solution and evenly spray into respectively in blank pipe tobacco (addition be pipe tobacco weight 0.4%), each tobacco sample after application of sample is placed in to the climatic chamber balance 48h of 22 ℃ of relative humidity 60%, temperature, make cigarette, put into again balance 48h，You panel of experts under the condition of 22 ℃ of relative humidity 60%, temperature it is carried out to sensory evaluating smoking's evaluation.
Smoking result shows, contrasting cigarette with propylene glycol compares, the cigarette flavor amount of having added above-mentioned monose ester compound increases, releases fragrant even, good with the fragrant Harmony of cigarette, aesthetic quality be improved significantly, showing that five carbon disclosed in this invention or six carbon monose Geraniol carbonic acid monoester class compounds have increases perfume quantity, releases fragrant all even effects that improves Sensory Quality of Cigarette.
Claims (4)
1. a class has the monose Geraniol carbonic acid monoester class compound of following general formula:
In general formula, O-R represents the residue of five carbon monose or six carbon monose; Geraniol carbonyl is positioned at any possible position of five carbon or six carbon monose;
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.
2. monose Geraniol carbonic acid monoester class compound as claimed in claim 1, it is characterized in that, described 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, 4-sorbitan ester, 1-O-Geraniol carbonyl-3, 6-sorbitan ester, 5-O-Geraniol carbonyl-D-core 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.
3. a preparation method for monose Geraniol carbonic acid monoester class compound as claimed in claim 1, is characterized in that, comprises the steps:
In reaction formula,
the protecting group that represents monose;
Steps A): take Geraniol as starting raw material, be dissolved in suitable solvent, add alkali and chlorine formylation reagent react, obtain chloroformic acid spiceleaf alcohol ester;
Step B): by steps A the chloroformic acid spiceleaf alcohol ester) obtaining is in suitable solvent and under acid binding agent existence condition, with five carbon monose or six carbon monose direct reaction, obtain 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, obtain corresponding monose Geraniol carbonic acid monoester class compound;
Or, adopt following steps to prepare monose Geraniol carbonic acid monoester class compound:
Steps A): take Geraniol as starting raw material, be dissolved in suitable solvent, add alkali and chlorine formylation reagent react, obtain chloroformic acid spiceleaf alcohol ester;
Step C): by steps A the chloroformic acid spiceleaf alcohol ester) obtaining, in suitable solvent and under acid binding agent existence condition, reacts with five carbon monose or six carbon monose with protecting group, obtains single Geraniol carbonyl-protecting group monose carbonats compound accordingly;
Step D): by step C the single Geraniol carbonyl-protecting group monose carbonats compound Deprotection) obtaining, obtains corresponding monose Geraniol carbonic acid monoester class compound;
Steps A), in, Chloroformylation solvent for use is selected from: C
3-8aliphatic ketone, C
5-10fat alkane or naphthenic hydrocarbon, DMF, 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 forms, methylene dichloride, chloroform, 1,2-ethylene dichloride, toluene or acetonitrile, reaction is carried out in single solvent or two kinds of mixed solvents, and the volume ratio of two kinds of mixed solvents is 1 ﹕ 0.1～10; Chloroformylation alkali used is: 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-phenylethylamine, N-methylmorpholine, N-methyl piperidine, triethylene diamine, 1,8-diazabicyclo [5,4,0] combination of 11 carbon-7-alkene or above-mentioned various alkali; Chlorine formylation reagent used 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;
Step B), in, reaction solvent for use is selected from: C
3-8aliphatic ketone, C
5-10fat alkane or naphthenic hydrocarbon, DMF, 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 forms, methylene dichloride, chloroform, 1,2-ethylene dichloride, toluene, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), water, pyridine or acetonitrile, reaction is carried out in single solvent or two kinds of mixed solvents, and the volume ratio of two kinds of mixed solvents is 1 ﹕ 0.1～10; Acid binding agent used is: triethylamine, Tributylamine, trioctylamine, pyridine, N, N-dimethyl-α-phenylethylamine, 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 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;
Step C), in, reaction solvent for use is selected from: C
3-8aliphatic ketone, C
5-10fat alkane or naphthenic hydrocarbon, DMF, 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 forms, methylene dichloride, chloroform, 1,2-ethylene dichloride, toluene, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), water, pyridine or acetonitrile, reaction is carried out in single solvent or two kinds of mixed solvents, and the volume ratio of two kinds of mixed solvents is 1 ﹕ 0.1～10; Acid binding agent used is: triethylamine, Tributylamine, trioctylamine, pyridine, N, N-dimethyl-α-phenylethylamine, TBAH, basic metal or alkaline earth metal hydroxides, basic metal or alkaline earth metal carbonate, basic metal or alkali metal bicarbonates; With five carbon monose of protecting group or the molar feed ratio of six carbon monose and chloroformic acid spiceleaf alcohol ester, be 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;
Step D), in, Deprotection acid used is: the aqueous hydrochloric acid that the acetic acid aqueous solution that the aqueous formic acid that the trifluoroacetic acid aqueous solution that content is 10%～95%, content are 10%～95%, content are 10%～95% or content are 1%～37%; The consumption of acid and the ratio of single Geraniol carbonyl-protecting group monose carbonats compound are: 0.5～50.0 ﹕ 1.0(L/mol); Temperature of reaction is-40 ℃～90 ℃; Reaction times is 1 hour～48 hours.
4. a purposes for monose Geraniol carbonic acid monoester class compound as claimed in claim 1, is as having the application that humid keeping performance has the cigarette humectant of flavouring and the effect of slowly-releasing spices concurrently.
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| CN102796146B (en) * | 2012-08-02 | 2014-05-14 | 河南中烟工业有限责任公司 | Humectant for cigarettes and preparation method thereof |
| CN102875611B (en) * | 2012-09-07 | 2014-12-10 | 河南中烟工业有限责任公司 | Humectants 1-O-carboxymethyl-D-furan mannose for cigarettes and preparation method of humectants 1-O-carboxymethyl-D-furan mannose |
| CN103467535B (en) * | 2013-06-19 | 2015-09-30 | 河南中烟工业有限责任公司 | A kind of humectant for smoke 1-O-hydroxyethyl-D-Fructose and preparation method thereof |
| CN106496149B (en) * | 2016-10-09 | 2019-04-26 | 湖北中烟工业有限责任公司 | The preparation method and applications of the latent fragrant monomer pyrazine -2- formate ester of cigarette |
| CN106496030B (en) * | 2016-10-09 | 2018-11-23 | 湖北中烟工业有限责任公司 | The preparation method and applications of the latent fragrant monomer P-methoxybenzoic acid esters of cigarette |
| CN106496147B (en) * | 2016-10-09 | 2019-04-26 | 湖北中烟工业有限责任公司 | The preparation method and applications of the latent fragrant monomer 5- methylpyrazine -2- formate ester of cigarette |
| CN111170867B (en) * | 2020-01-14 | 2023-04-28 | 深圳怀赤科技有限公司 | Geraniol derivative, preparation method thereof and application of geraniol derivative as slow-release spice |
| CN112625018A (en) * | 2020-12-10 | 2021-04-09 | 河南中烟工业有限责任公司 | 2, 3-dihydro-3-hydroxy-6-methyl-4H-pyran-4-one-5-O-linalyl carbonate and application thereof |
| KR20230073440A (en) * | 2021-11-18 | 2023-05-26 | 주식회사 케이티앤지 | New flavoring agent, composition and article comprising same |
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