CN102286033B - Monosaccharide beta-ionol carbonate diester compound as well as preparation method and application thereof - Google Patents
Monosaccharide beta-ionol carbonate diester compound as well as preparation method and application thereof Download PDFInfo
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- CN102286033B CN102286033B CN201110259988.XA CN201110259988A CN102286033B CN 102286033 B CN102286033 B CN 102286033B CN 201110259988 A CN201110259988 A CN 201110259988A CN 102286033 B CN102286033 B CN 102286033B
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- 0 C[C@](C=CC1=C(C)CCCC1(C)C)OC(*C(C(C(C(*C(OC(C)C=CC(C(C)(C)CCC1)=C1C(C)=NC)=O)O)O)O)O)=O Chemical compound C[C@](C=CC1=C(C)CCCC1(C)C)OC(*C(C(C(C(*C(OC(C)C=CC(C(C)(C)CCC1)=C1C(C)=NC)=O)O)O)O)O)=O 0.000 description 1
Abstract
The invention relates to cigarette humectants and discloses a monosaccharide beta-ionol carbonate diester compound, and also discloses a preparation method of the compound and an application of the compound in the cigarette humectant, wherein the moisture retention effect, the moistureproof effect, the slow-release spice effect of the compound as the cigarette humectant are tested. Based on the test, the monosaccharide beta-ionol carbonate diester compound has the moisture retention capability on the cigarettes and has the functions of increasing redolence, uniformly releasing the redolence and improving the sensory quality of the cigarettes. In FORMULA shown in the description, O-R-O represents residue of C5 monosaccharide or C6 monosaccharide; and two beta-ionol carbonate ester structural units are arranged at any two proper positions of the C5 or C6 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 β-ionol carbonic acid di-esters 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 β-ionol carbonic acid di-esters compound.
Second object of the present invention is to disclose the preparation method of such monose β-ionol carbonic acid di-esters compound.
The 3rd object of the present invention is to disclose such monose β-ionol carbonic acid di-esters 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 β-ionol carbonic acid di-esters compound with following general formula:
Wherein, O-R-O represents the residue of five carbon monose or six carbon monose; Two β-ionol carbonate structural units are positioned at any two possible positions 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 β-ionol carbonic acid di-esters compound as above, can prepare with the following method:
Take β-ionol 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 β-ionol esters; Then in suitable solvent and under acid binding agent existence condition, corresponding chloroformic acid β-ionol esters reacts with five carbon monose or derivatives thereofs or six carbon monose or derivatives thereofs, through aftertreatment, make β-ionol carbonic acid dibasic acid esters and β-ionol carbonic acid polyesters mixture of corresponding five carbon or six carbon monose, gained dibasic acid esters and polyesters mixture, through recrystallization or column chromatography purification, obtain corresponding monose β-ionol carbonic acid di-esters compound.
Its concrete preparation method is described below:
Steps A): take β-ionol as starting raw material is starting raw material, be dissolved in suitable solvent, add alkali and chlorine formylation reagent react, obtain chloroformic acid β-ionol esters; 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 β-ionol, 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 β-ionol esters) obtaining is in suitable solvent and under acid binding agent existence condition, react with five carbon monose or derivatives thereofs or six carbon monose or derivatives thereofs, obtain β-ionol carbonic acid dibasic acid esters and β-ionol carbonic acid polyesters mixture of corresponding five carbon or six carbon monose, through conventional recrystallization or column chromatography purification, obtain corresponding monose β-ionol carbonic acid di-esters 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 derivatives thereofs or six carbon monose or derivatives thereofs and chloroformic acid β-ionol esters is 1.0: 0.2～10.0, and preferably molar feed ratio is 1.0: 2.0～4.0; The molar feed ratio of acid binding agent and chloroformic acid β-ionol esters is 1.0～10.0: 1.0, and preferably molar feed ratio is 1.0～3.0: 1.0; Temperature of reaction is-40 ℃～120 ℃, 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.
The 3rd object of the present invention is achieved in that
Monose β-ionol carbonic acid di-esters 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 β-ionol carbonic acid di-esters 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 β-ionol carbonic acid di-esters 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 β-ionol carbonic acid di-esters 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 β-ionol 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, product toxicological harmless after monose β-ionol carbonic acid di-esters cigarette humectant burning disclosed in this invention, use safety, be more conducive to the security of sucking of tobacco, be 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-β-ionol esters 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 β-ionol 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-β-ionol esters, without purifying, can be used for the next step, quantitative yield.
Embodiment 2: chloroformic acid-β-ionol esters 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-β-ionol esters, without purifying, can be used for the next step, quantitative yield.
Embodiment 3:3, the preparation of 6-bis--O-β-ionol carbonyl-D-glucopyanosyl carbonic ether (Compound I)
Get chloroformic acid-β-ionol esters dichloromethane solution 0.15mol that embodiment 1 makes, be added dropwise to the D-Glucose methyl glucoside 9.7g (0.05mol) that is cooled to-5～0 ℃, in triethylamine 20.2g (0.20mol) and methylene dichloride 100ml mixed solution, stirring at room reaction 12h, after reaction finishes, solid is separated out in filtration, filtrate decompression is steamed and is desolventized, resistates is dissolved in to methylene dichloride 200ml, add 20% aqueous hydrochloric acid 40ml, stirring at room 2h, organic layer is successively with saturated aqueous sodium carbonate 50ml and saturated aqueous common salt 50ml washing, gained dichloromethane solution is through anhydrous Na
2sO
4dry, filter, remove methylene dichloride under reduced pressure, resistates is through purification by silica gel column chromatography (elutriant: chloroform/methanol=30/1, v/v), obtains 3,6-, bis--O-β-ionol carbonyl-D-glucopyanosyl carbonic ether, yield 55.0%, HR-TOFMS (+Q) m/z:643.3455 ([C
34h
52o
10+ Na]
+calculated value: 643.3458).
Embodiment 4:2, the preparation of 3-bis--O-β-ionol carbonyl-D-glucopyanosyl carbonic ether (Compound I I)
Get chloroformic acid β-ionol esters toluene solution 0.15mol that embodiment 2 makes, be added dropwise to be cooled to-5～0 ℃ 4, 6-O-isopropylidene-D-Glucose methyl glucoside 0.05mol, in pyridine 0.20mol and ethyl acetate 100ml mixed solution, stirring at room reaction 18h, after reaction finishes, solid is separated out in filtration, filtrate decompression is steamed and is desolventized, resistates is dissolved in to ethyl acetate 200ml, add 20% aqueous hydrochloric acid 40ml, stirring at room 2h, organic layer is successively with saturated aqueous sodium carbonate 50ml and saturated aqueous common salt 50ml washing, gained ethyl acetate solution is through anhydrous Na
2sO
4dry, filter, remove ethyl acetate under reduced pressure, resistates is through purification by silica gel column chromatography (elutriant: chloroform/methanol=25/1, v/v), obtains 2,3-, bis--O-β-ionol carbonyl-D-glucopyanosyl carbonic ether, yield 80.0%, HR-TOFMS (+Q) m/z:643.3462 ([C
34h
52o
10+ Na]
+calculated value: 643.3458).
Embodiment 5:1, the preparation of 6-bis--O-β-ionol carbonyl-D-gala pyranose carbonic ether (compound III)
Operating process, with embodiment 3, just substitutes D-Glucose methyl glucoside with D-semi-lactosi, methylene dichloride substitutes with pyridine, obtains 1,6-, bis--O-β-ionol carbonyl-D-gala pyranose carbonic ether, yield 25.0%; HR-TOFMS (+Q) m/z:643.3451 ([C
34h
52o
10+ Na]
+calculated value: 643.3458).
Embodiment 6:2, the preparation of 3-bis--O-β-ionol carbonyl-D-gala pyranose carbonic ether (compound IV)
Operating process, with embodiment 3, just substitutes D-Glucose methyl glucoside with 4,6-O-isopropylidene-D-semi-lactosi methyl glucoside, triethylamine substitutes with pyridine, obtains 2,3-, bis--O-β-ionol carbonyl-D-gala pyranose carbonic ether, yield 80.0%; HR-TOFMS (+Q) m/z:643.3453 ([C
34h
52o
10+ Na]
+calculated value: 643.3458).
Embodiment 7:2, the preparation of 6-bis--O-β-ionol carbonyl-D-gala pyranose carbonic ether (compound V)
Operating process, with embodiment 4, just substitutes 4,6-O-isopropylidene-D-Glucose methyl glucoside with 3,4-O-isopropylidene-D-semi-lactosi methyl glucoside, obtain 2,6-, bis--O-β-ionol carbonyl-D-gala pyranose carbonic ether, yield 73.0%; HR-TOFMS (+Q) m/z:643.3459 ([C
34h
52o
10+ Na]
+calculated value: 643.3458).
Embodiment 8:2, the preparation of 3-bis--O-β-ionol carbonyl-D-mannopyranose carbonic ether (compound VI)
Operating process, with embodiment 4, just substitutes 4,6-O-isopropylidene-D-Glucose methyl glucoside with 4,6-O-isopropylidene-D-MANNOSE methyl glucoside, obtain 2,3-, bis--O-β-ionol carbonyl-D-mannopyranose carbonic ether, yield 66.0%; HR-TOFMS (+Q) m/z:643.3455 ([C
34h
52o
10+ Na]
+calculated value: 643.3458).
Embodiment 9:4, the preparation of 6-bis--O-β-ionol carbonyl-D-mannopyranose carbonic ether (compound VI I)
Operating process, with embodiment 4, just substitutes 4,6-O-isopropylidene-D-Glucose methyl glucoside with 2,3-O-isopropylidene-D-MANNOSE methyl glucoside, obtain 4,6-, bis--O-β-ionol carbonyl-D-mannopyranose carbonic ether, yield 77.0%; HR-TOFMS (+Q) m/z:643.3457 ([C
34h
52o
10+ Na]
+calculated value: 643.3458).
Embodiment 10:1, the preparation of 6-bis--O-β-ionol carbonyl-D-sorb furanose carbonic ether (compound VI II)
Operating process, with embodiment 3, just substitutes D-Glucose methyl glucoside with D-sorbose, methylene dichloride substitutes with pyridine, obtains 1,6-, bis--O-β-ionol carbonyl-D-sorb furanose carbonic ether, yield 32.0%; HR-TOFMS (+Q) m/z:643.3463 ([C
34h
52o
10+ Na]
+calculated value: 643.3458).
Embodiment 11:1, the preparation of 6-bis--O-β-ionol carbonyl-D-fruit furanose carbonic ether (Compound I X)
Operating process, with embodiment 3, just substitutes D-Glucose methyl glucoside with D-Fructose, methylene dichloride substitutes with pyridine, obtains 1,6-, bis--O-β-ionol carbonyl-D-fruit furanose carbonic ether, yield 35.0%; HR-TOFMS (+Q) m/z:643.3455 ([C
34h
52o
10+ Na]
+calculated value: 643.3458).
Embodiment 12:1, the preparation of 6-bis--O-β-ionol carbonyl-N.F,USP MANNITOL carbonic ether (compounds X)
Operating process, with embodiment 3, just substitutes D-Glucose methyl glucoside with N.F,USP MANNITOL, methylene dichloride substitutes with pyridine, obtains 1,6-, bis--O-β-ionol carbonyl-N.F,USP MANNITOL carbonic ether, yield 74.0%; HR-TOFMS (+Q) m/z:645.3610 ([C
34h
54o
10+ Na]
+calculated value: 645.3615).
Embodiment 13:1, the preparation of 6-bis--O-β-ionol carbonyl-sorbyl alcohol carbonic ether (compounds X I)
Operating process, with embodiment 3, just substitutes D-Glucose methyl glucoside with sorbyl alcohol, methylene dichloride substitutes with pyridine, obtains 1,6-, bis--O-β-ionol carbonyl-sorbyl alcohol carbonic ether, yield 63.0%; HR-TOFMS (+Q) m/z:645.3613 ([C
34h
54o
10+ Na]
+calculated value: 645.3615).
Embodiment 14:3, the preparation of 5-bis--O-β-ionol carbonyl-D-wood furanose carbonic ether (compounds X II)
Operating process, with embodiment 3, just substitutes 1,2-O-isopropylidene for D-Glucose methyl glucoside-D-wood furanose, obtains 3,5-, bis--O-β-ionol carbonyl-D-wood furanose carbonic ether, yield 60.0%; HR-TOFMS (+Q) m/z:613.3356 ([C
33h
50o
9+ Na]
+calculated value: 613.3353).
Embodiment 15:3, the preparation of 5-bis--O-β-ionol carbonyl-D-core furanose carbonic ether (compounds X III)
Operating process, with embodiment 3, just substitutes D-Glucose methyl glucoside with 1,2-O-isopropylidene-D-core furanose, obtain 3,5-, bis--O-β-ionol carbonyl-D-core furanose carbonic ether, yield 55.0%; HR-TOFMS (+Q) m/z:613.3350 ([C
33h
50o
9+ Na]
+calculated value: 613.3353).
Embodiment 16:3, the preparation of 5-bis--O-β-ionol carbonyl-D-lysol furanose carbonic ether (compounds X IV)
Operating process, with embodiment 3, just substitutes D-Glucose methyl glucoside with 1,2-O-isopropylidene-D-lysol furanose, obtain 3,5-, bis--O-β-ionol carbonyl-D-lysol furanose carbonic ether, yield 68.0%; HR-TOFMS (+Q) m/z:613.3359 ([C
33h
50o
9+ Na]
+calculated value: 613.3353).
Embodiment 17: 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 β-ionol carbonic acid monoester class compounds (I～XIV) 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 β-ionol carbonic acid di-esters 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 β-ionol carbonic acid di-esters compounds have good humectation and moisture-proof role to pipe tobacco in various degree.
Embodiment 18: 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 β-ionol carbonic acid di-esters compounds (I～XIV) 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 β-ionol carbonic acid di-esters compounds have certain effect that slows down flavour ingredient volatilization in pipe tobacco.
Embodiment 19: 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 β-ionol carbonic acid di-esters compounds (I～XIV) 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 shows, these compounds all have the aroma components such as β-ionol to produce at 200 ℃, 450 ℃ and 700 ℃, show that five carbon disclosed in this invention or six carbon monose β-ionol carbonic acid di-esters compounds have the effect that thermo-cracking discharges aroma component.
Embodiment 20: sensory evaluating smoking evaluates
For five carbon disclosed in this invention or six carbon monose β-ionol carbonic acid di-esters compounds (I～XIV), 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 under the condition of 22 ℃ of relative humidity 60%, temperature, by panel of experts, 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 β-ionol carbonic acid di-esters compounds have increases perfume quantity, releases fragrant all even effects that improves Sensory Quality of Cigarette.
Claims (4)
1. a class has monose β-ionol carbonic acid di-esters compound of following general formula:
In general formula, O-R-O represents the residue of five carbon monose or six carbon monose; Two β-ionol carbonate structural units are positioned at any two possible positions of five carbon or six carbon monose;
Above-mentioned five carbon monose are: wood sugar, ribose, pectinose, lyxose, ribulose or xylulose, six carbon monose are: glucose, semi-lactosi, seminose, sorbose, gulose, fructose, N.F,USP MANNITOL, sorbyl alcohol, 1,4-anhydrous sorbitol or 3,6-anhydrous sorbitol.
2. monose β-ionol carbonic acid di-esters compound as claimed in claim 1, it is characterized in that, described compound is selected from: 3, 6-bis--O-β-ionol carbonyl-D-glucopyanosyl carbonic ether, 2, 3-bis--O-β-ionol carbonyl-D-glucopyanosyl carbonic ether, 1, 6-bis--O-β-ionol carbonyl-D-gala pyranose carbonic ether, 2, 3-bis--O-β-ionol carbonyl-D-gala pyranose carbonic ether, 2, 6-bis--O-β-ionol carbonyl-D-gala pyranose carbonic ether, 2, 3-bis--O-β-ionol carbonyl-D-mannopyranose carbonic ether, 4, 6-bis--O-β-ionol carbonyl-D-mannopyranose carbonic ether, 1, 6-bis--O-β-ionol carbonyl-D-sorb furanose carbonic ether, 1, 6-bis--O-β-ionol carbonyl-D-fruit furanose carbonic ether, 1, 6-bis--O-β-ionol carbonyl-N.F,USP MANNITOL carbonic ether, 1, 6-bis--O-β-ionol carbonyl-sorbyl alcohol carbonic ether, 3, 5-bis--O-β-ionol carbonyl-D-wood furanose carbonic ether, 3, 5-bis--O-β-ionol carbonyl-D-core furanose carbonic ether or 3, 5-bis--O-β-ionol carbonyl-D-lysol furanose carbonic ether.
3. a preparation method for monose β-ionol carbonic acid di-esters compound as claimed in claim 1, is characterized in that, comprises the steps:
In formula, HO-R-OH represents D-Glucose methyl glucoside, 4,6-O-isopropylidene-D-Glucose methyl glucoside, D-semi-lactosi, 4,6-O-isopropylidene-D-semi-lactosi methyl glucoside, 3,4-O-isopropylidene-D-semi-lactosi methyl glucoside, 4,6-O-isopropylidene-D-MANNOSE methyl glucoside, 2,3-O-isopropylidene-D-MANNOSE methyl glucoside, D-sorbose, D-Fructose, N.F,USP MANNITOL, sorbyl alcohol, 1,2-O-isopropylidene-D-wood furanose, 1,2-O-isopropylidene-D-core furanose or 1,2-O-isopropylidene-D-lysol furanose;
Steps A): take β-ionol as starting raw material, be dissolved in suitable solvent, add alkali and chlorine formylation reagent react, obtain chloroformic acid β-ionol esters; Wherein, Chloroformylation solvent for use is selected from: methylene dichloride and toluene; Chloroformylation alkali used is: pyridine or sodium bicarbonate; Chlorine formylation reagent used is: superpalite or two (trichloromethyl) carbonic ether; The molar feed ratio of β-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;
Step B): by steps A the chloroformic acid β-ionol esters) obtaining reacts with HO-R-OH in suitable solvent He under acid binding agent existence condition, obtain β-ionol carbonic acid dibasic acid esters and β-ionol carbonic acid polyesters mixture of corresponding five carbon or six carbon monose, through conventional recrystallization or column chromatography purification, obtain corresponding monose β-ionol carbonic acid di-esters compound; Wherein, reaction solvent for use is selected from: methylene dichloride, pyridine and ethyl acetate; Acid binding agent used is: triethylamine or pyridine; The molar feed ratio of described HO-R-OH and chloroformic acid β-ionol esters is 1.0:0.2～10.0; The molar feed ratio of acid binding agent and chloroformic acid β-ionol esters is 1.0～10.0:1.0; Temperature of reaction is-40 ℃～120 ℃; Condensation reaction time is 1 hour～48 hours.
4. a purposes for monose β-ionol carbonic acid di-esters 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5172705A (en) * | 1991-09-25 | 1992-12-22 | Philip Morris Incorporated | Smoking compositions containing an oxalate flavorant-release additive |
| CN1434016A (en) * | 2003-01-24 | 2003-08-06 | 华宝香化科技发展（上海）有限公司 | Method for producing perfume using ionol ester as raw material by thermo-wacking rectifying |
| CN101974042A (en) * | 2010-10-29 | 2011-02-16 | 川渝中烟工业公司 | Mono-pentose or hexose-(E)-3-(furan-2-yl) acrylic acid diester compound and preparation method and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5172705A (en) * | 1991-09-25 | 1992-12-22 | Philip Morris Incorporated | Smoking compositions containing an oxalate flavorant-release additive |
| CN1434016A (en) * | 2003-01-24 | 2003-08-06 | 华宝香化科技发展（上海）有限公司 | Method for producing perfume using ionol ester as raw material by thermo-wacking rectifying |
| CN101974042A (en) * | 2010-10-29 | 2011-02-16 | 川渝中烟工业公司 | Mono-pentose or hexose-(E)-3-(furan-2-yl) acrylic acid diester compound and preparation method and use thereof |
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