Summary of the invention
The object of the present invention is to provide a kind of monose Geraniol carbonic acid di-esters compound.
Second purpose of the present invention is to disclose the preparation method of such monose Geraniol carbonic acid di-esters compound.
The 3rd purpose of the present invention is to disclose such monose Geraniol carbonic acid di-esters compound as having the purposes that the humectation performance has the new cigarette humectant of flavouring and the effect of slowly-releasing spices concurrently.
The objective of the invention is to realize like this:
A kind of monose Geraniol carbonic acid di-esters compound with following general formula:
Wherein, O-R-O represents the residue of five carbon monose or six carbon monose; Two Geraniol 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: glucose, semi-lactosi, seminose, sorbose, gulose, fructose, N.F,USP MANNITOL, sorbyl alcohol, 1; 4-anhydrous sorbitol or 3, the 6-anhydrous sorbitol.
Second purpose of the present invention is achieved in that
A kind of preparation method of aforesaid monose Geraniol carbonic acid di-esters compound is characterized in that available following method preparation:
With the Geraniol is starting raw material, and it is dissolved in the suitable solvent, adds alkali and chlorine formylation reagent, after reaction for some time, through aftertreatment, makes chloroformic acid spiceleaf alcohol ester; Then in suitable solvent and under the acid binding agent existence condition; Chloroformic acid spiceleaf alcohol ester and five carbon monose or derivatives thereofs or the reaction of six carbon monose or derivatives thereofs; Through aftertreatment; Make the Geraniol carbonic acid dibasic acid esters and the Geraniol carbonic acid polyesters mixture of corresponding five carbon or six carbon monose, gained dibasic acid esters and polyesters mixture promptly get corresponding monose Geraniol carbonic acid di-esters compound through recrystallization or column chromatography purification.
Its concrete preparation method is described below:
Steps A): with the Geraniol is starting raw material, and it is dissolved in the suitable solvent, adds alkali and chlorine formylation reagent react, gets chloroformic acid spiceleaf alcohol ester; Wherein, chlorine formylation reaction solvent for use is selected from: C
3-8Alkanone, C
5-10Fat alkane or naphthenic hydrocarbon, N, dinethylformamide, ether, isopropyl ether, MTBE, THF, glycol dimethyl ether, sherwood oil, C
1-6Lipid acid and C
1-6Ester that Fatty Alcohol(C12-C14 and C12-C18) forms, methylene dichloride, chloroform, 1; 2-ethylene dichloride, toluene or acetonitrile, reaction can be carried out in single solvent, also can in two kinds of mixed solvents, carry out; The volume ratio of two kinds of mixed solvents is 1: 0.1~10, and preferred solvent is: methylene dichloride, chloroform, acetone or toluene;
Chlorine formylation reacts used alkali: basic metal or alkaline earth metal hydroxides, basic metal or alkaline earth metal carbonate, basic metal or alkali metal bicarbonates, piperidines, Pyrrolidine, triethylamine, Tributylamine, trioctylamine, pyridine, N; N-dimethyl--α-Ben Yian, N-methylmorpholine, N-methyl piperidine, triethylene diamine, 1; 8-diazabicyclo [5; 4,0] combination of 11 carbon-7-alkene or above-mentioned various alkali, preferred bases is: sodium hydrogencarbonate, triethylamine or pyridine;
Used chlorine formylation reagent is: phosgene, superpalite or two (trichloromethyl) carbonic ether;
The molar feed ratio of Geraniol, chlorine formylation reagent and alkali is 1.0: 0.2~10.0: 0.5~20.0, and preferred molar feed ratio is 1.0: 0.3~2.0: 1.0~6.0; Temperature of reaction is-40 ℃~130 ℃, and preferable reaction temperature is-20 ℃~40 ℃; Reaction times is 20 minutes~48 hours, and the preferred reaction time is 1 hour~24 hours.
Step B): by steps A the chloroformic acid spiceleaf alcohol ester that) obtains is in suitable solvent and under the acid binding agent existence condition; With five carbon monose or derivatives thereofs or the reaction of six carbon monose or derivatives thereofs; Get the Geraniol carbonic acid dibasic acid esters and the Geraniol carbonic acid polyesters mixture of corresponding five carbon or six carbon monose; Through conventional recrystallization or column chromatography purification, get corresponding monose Geraniol carbonic acid di-esters compound;
Wherein, the reaction solvent for use is selected from: C
3-8Alkanone, C
5-10Fat alkane or naphthenic hydrocarbon, N, dinethylformamide, ether, isopropyl ether, MTBE, THF, glycol dimethyl ether, sherwood oil, C
1-6Lipid acid and C
1-6Ester that Fatty Alcohol(C12-C14 and C12-C18) forms, methylene dichloride, chloroform, 1; 2-ethylene dichloride, toluene, N-Methyl pyrrolidone, DMSO 99.8MIN., water, pyridine or acetonitrile; Reaction can be carried out in single solvent, also can in two kinds of mixed solvents, carry out, and the volume ratio of two kinds of mixed solvents is 1: 0.1~10; Preferred solvent is: THF, N, dinethylformamide, methylene dichloride, ETHYLE ACETATE or pyridine;
Used acid binding agent is: triethylamine, Tributylamine, trioctylamine, pyridine, N; N-dimethyl--α-Ben Yian, TBAH, basic metal or alkaline earth metal hydroxides, basic metal or alkaline earth metal carbonate, basic metal or alkali metal bicarbonates, preferred acid binding agent is: triethylamine, pyridine or sodium hydrogencarbonate;
The molar feed ratio of five carbon monose or derivatives thereofs or six carbon monose or derivatives thereofs and chloroformic acid spiceleaf alcohol ester is 1.0: 0.2~10.0, and preferred molar feed ratio is 1.0: 2.0~4.0; The molar feed ratio of acid binding agent and chloroformic acid spiceleaf alcohol ester is 1.0~10.0: 1.0, and preferred molar feed ratio is 1.0~3.0: 1.0; Temperature of reaction is-40 ℃~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 purpose of the present invention is achieved in that
The disclosed monose Geraniol of the present invention carbonic acid di-esters 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 cigarette surface formation profit.
Compared with prior art, beneficial effect of the present invention is following:
1, the disclosed monose Geraniol of the present invention carbonic acid di-esters cigarette humectant can have humectation and moistureproof two kinds of effects simultaneously through the bilayer protective membrane of being separated by at cigarette surface formation profit; The speed that in the exsiccant climatope, dries out through the cigarette that this type humectant was handled is slow; And the speed that in the climatope of humidity, absorbs moisture is also slow, can effectively slow down the variation of tobacco moisture with envrionment conditions.
2, the disclosed monose Geraniol of the present invention carbonic acid di-esters cigarette humectant also can be separated by the bilayer protective membrane and the volatilization that significantly slow down flavour ingredient in the tobacco through the profit that forms on tobacco surface, thereby has certain slowly-releasing spices effect.
3, the fragrance of the disclosed monose Geraniol of the present invention carbonic acid di-esters cigarette humectant own is less or do not have fragrance, but in the cigarette burning 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 cigarette, and Geraniol is widely used in the actual production as the cigarette deodorant tune, and therefore, the present invention's disclosed this type cigarette humectant and tobacco have compatibleness preferably, and be safe.
4, with present cigarette industry on widely used Ucar 35 or glycerine compare, the product toxicological harmless after the burning of the disclosed monose Geraniol of the present invention carbonic acid di-esters cigarette humectant, safe in utilization, more help the security of sucking of cigarette, be easy to apply.
Embodiment
Can further describe the present invention through following embodiment, yet scope of the present invention is not limited to following embodiment.One of skill in the art can understand, and under the prerequisite that does not deviate from the spirit and scope of the present invention, can carry out various variations and modification to the present invention.
Embodiment 1: chloroformic acid spiceleaf alcohol ester synthetic
In reaction flask, add 2000ml CH
2Cl
2With two (trichloromethyl) carbonic ether 129g (0.44mol), after stirring at room to solid entirely dissolves, reaction flask is put during cryosel bathes, be cooled to-10 ℃ after; Add Geraniol 1.28mol, after the dissolving, drip the 200ml pyridine fully, the control rate of addition; Make reacting liquid temperature maintain 0~5 ℃, drip and finish, reaction solution is warming up to room temperature naturally, stirring reaction spends the night; Promptly get the dichloromethane solution of chloroformic acid spiceleaf alcohol ester, need not purifying and promptly can be used for step reaction down, quantitative yield.
Embodiment 2: chloroformic acid spiceleaf alcohol ester synthetic
Operating process just substitutes two (trichloromethyl) carbonic ethers with embodiment 1 with superpalite, pyridine substitutes with sodium hydrogencarbonate, CH
2Cl
2Substitute with toluene, get the toluene solution of chloroformic acid spiceleaf alcohol ester, need not purifying and promptly can be used for step reaction down, quantitative yield.
Embodiment 3:3, the preparation of 6-two-O-Geraniol carbonyl-D-glucopyanosyl carbonic ether (compound I)
Get the chloroformic acid spiceleaf alcohol ester dichloromethane solution 0.15mol that embodiment 1 makes, be added dropwise in D-glucose methyl glucoside 9.7g (0.05mol), triethylamine 20.2g (0.20mol) and the methylene dichloride 100ml mixed solution that is cooled to-5~0 ℃, stirring at room reaction 12h; After reaction finishes; Solid is separated out in filtration, and filtrate decompression is steamed and desolventized, and resistates is dissolved in methylene dichloride 200ml; Add 20% aqueous hydrochloric acid 40ml; With saturated aqueous sodium carbonate 50ml and saturated aqueous common salt 50ml washing, the gained dichloromethane solution is through anhydrous Na successively for stirring at room 2h, organic layer
2SO
4Drying is filtered, and removes methylene dichloride under reduced pressure, and (elutriant: chloroform/methanol=30/1 v/v), gets 3,6-two-O-Geraniol carbonyl-D-glucopyanosyl carbonic ether, yield 60.0% to resistates through purification by silica gel column chromatography; HR-TOFMS (+Q) m/z:563.2830 ([C
28H
44O
10+ Na]
+Calculated value: 563.2832).
Embodiment 4:2, the preparation of 3-two-O-Geraniol carbonyl-D-glucopyanosyl carbonic ether (compound I I)
Get the chloroformic acid spiceleaf alcohol ester toluene solution 0.15mol that embodiment 2 makes, be added dropwise to be cooled to-5~0 ℃ 4, in 6-O-isopropylidene-D-glucose methyl glucoside 0.05mol, pyridine 0.20mol and the ETHYLE ACETATE 100ml mixed solution; Stirring at room reaction 15h after reaction finishes, filters and separates out solid; Filtrate decompression is steamed and is desolventized; Resistates is dissolved in ETHYLE ACETATE 200ml, adds 20% aqueous hydrochloric acid 40ml, stirring at room 2h; With saturated aqueous sodium carbonate 50ml and saturated aqueous common salt 50ml washing, the gained ethyl acetate solution is through anhydrous Na successively for organic layer
2SO
4Drying is filtered, and removes ETHYLE ACETATE under reduced pressure, and (elutriant: chloroform/methanol=30/1 v/v), gets 2,3-two-O-Geraniol carbonyl-D-glucopyanosyl carbonic ether, yield 85.0% to resistates through purification by silica gel column chromatography; HR-TOFMS (+Q) m/z:563.2825 ([C
28H
44O
10+ Na]
+Calculated value: 563.2832).
Embodiment 5:1, the preparation of 6-two-O-Geraniol carbonyl-D-gala pyranose carbonic ether (compound III)
Operating process just substitutes D-glucose methyl glucoside with embodiment 3 with the D-semi-lactosi, methylene dichloride substitutes with pyridine, gets 1,6-two-O-Geraniol carbonyl-D-gala pyranose carbonic ether, yield 18.0%; HR-TOFMS (+Q) m/z:563.2835 ([C
28H
44O
10+ Na]
+Calculated value: 563.2832).
Embodiment 6:2, the preparation of 3-two-O-Geraniol carbonyl-D-gala pyranose carbonic ether (compound IV)
Operating process is with embodiment 3, just with D-glucose methyl glucoside with 4,6-O-isopropylidene-D-semi-lactosi methyl glucoside substitutes, triethylamine substitutes with pyridine, must 2,3-two-O-Geraniol carbonyl-D-gala pyranose carbonic ether, yield 83.0%; HR-TOFMS (+Q) m/z:563.2831 ([C
28H
44O
10+ Na]
+Calculated value: 563.2832).
Embodiment 7:2, the preparation of 6-two-O-Geraniol carbonyl-D-gala pyranose carbonic ether (compound V)
Operating process is with embodiment 4, and just with 4,6-O-isopropylidene-D-glucose methyl glucoside is with 3, and 4-O-isopropylidene-D-semi-lactosi methyl glucoside substitutes, and gets 2,6-two-O-Geraniol carbonyl-D-gala pyranose carbonic ether, yield 77.0%; HR-TOFMS (+Q) m/z:563.2839 ([C
28H
44O
10+ Na]
+Calculated value: 563.2832).
Embodiment 8:2, the preparation of 3-two-O-Geraniol carbonyl-D-mannopyranose carbonic ether (compound VI)
Operating process is with embodiment 4, and just with 4,6-O-isopropylidene-D-glucose methyl glucoside is with 4, and 6-O-isopropylidene-D-seminose methyl glucoside substitutes, and gets 2,3-two-O-Geraniol carbonyl-D-mannopyranose carbonic ether, yield 70.0%; HR-TOFMS (+Q) m/z:563.2835 ([C
28H
44O
10+ Na]
+Calculated value: 563.2832).
Embodiment 9:4, the preparation of 6-two-O-Geraniol carbonyl-D-mannopyranose carbonic ether (compound VI I)
Operating process is with embodiment 4, and just with 4,6-O-isopropylidene-D-glucose methyl glucoside is with 2, and 3-O-isopropylidene-D-seminose methyl glucoside substitutes, and gets 4,6-two-O-Geraniol carbonyl-D-mannopyranose carbonic ether, yield 75.0%; HR-TOFMS (+Q) m/z:563.2829 ([C
28H
44O
10+ Na]
+Calculated value: 563.2832).
Embodiment 10:1, the preparation of 6-two-O-Geraniol carbonyl-D-sorb furanose carbonic ether (compound VIII)
Operating process just substitutes D-glucose methyl glucoside with embodiment 3 with the D-sorbose, methylene dichloride substitutes with pyridine, gets 1,6-two-O-Geraniol carbonyl-D-sorb furanose carbonic ether, yield 35.0%; HR-TOFMS (+Q) m/z:563.2825 ([C
28H
44O
10+ Na]
+Calculated value: 563.2832).
Embodiment 11:1, the preparation of 6-two-O-Geraniol carbonyl-D-fruit furanose carbonic ether (compound I X)
Operating process just substitutes D-glucose methyl glucoside with embodiment 3 with D-fructose, methylene dichloride substitutes with pyridine, gets 1,6-two-O-Geraniol carbonyl-D-fruit furanose carbonic ether, yield 30.0%; HR-TOFMS (+Q) m/z:563.2840 ([C
28H
44O
10+ Na]
+Calculated value: 563.2832).
Embodiment 12:1, the preparation of 6-two-O-Geraniol carbonyl-N.F,USP MANNITOL carbonic ether (compounds X)
Operating process just substitutes D-glucose methyl glucoside with embodiment 3 with N.F,USP MANNITOL, methylene dichloride substitutes with pyridine, gets 1,6-two-O-Geraniol carbonyl-N.F,USP MANNITOL carbonic ether, yield 70.0%; HR-TOFMS (+Q) m/z:565.2990 ([C
28H
46O
10+ Na]
+Calculated value: 565.2989).
Embodiment 13:1, the preparation of 6-two-O-Geraniol carbonyl-sorbyl alcohol carbonic ether (compounds X I)
Operating process just substitutes D-glucose methyl glucoside with embodiment 3 with sorbyl alcohol, methylene dichloride substitutes with pyridine, gets 1,6-two-O-Geraniol carbonyl-sorbyl alcohol carbonic ether, yield 60.0%; HR-TOFMS (+Q) m/z:565.2985 ([C
28H
46O
10+ Na]
+Calculated value: 565.2989).
Embodiment 14:3, the preparation of 5-two-O-Geraniol carbonyl-D-wood furanose carbonic ether (compounds X II)
Operating process is with embodiment 3, just with D-glucose methyl glucoside with 1,2-O-isopropylidene-D-wood furanose substitutes, 3, the wooden furanose carbonic ether of 5-two-O-Geraniol carbonyl-D-, yield 63.0%; HR-TOFMS (+Q) m/z:533.2722 ([C
27H
42O
9+ Na]
+Calculated value: 533.2727).
Embodiment 15:3, the preparation of 5-two-O-Geraniol carbonyl-D-nuclear furanose carbonic ether (compounds X III)
Operating process is with embodiment 3, just with D-glucose methyl glucoside with 1,2-O-isopropylidene-D-nuclear furanose substitutes, 3,5-two-O-Geraniol carbonyl-D-examines furanose carbonic ether, yield 60.0%; HR-TOFMS (+Q) m/z:533.2726 ([C
27H
42O
9+ Na]
+Calculated value: 533.2727).
Embodiment 16:3, the preparation of 5-two-O-Geraniol carbonyl-D-lysol furanose carbonic ether (compounds X IV)
Operating process is with embodiment 3, just with D-glucose methyl glucoside with 1,2-O-isopropylidene-D-lysol furanose substitutes, must 3,5-two-O-Geraniol carbonyl-D-lysol furanose carbonic ether, yield 70.0%; HR-TOFMS (+Q) m/z:533.2730 ([C
27H
42O
9+ Na]
+Calculated value: 533.2727).
Embodiment 17: humectation and moisture-proof role test
Is contrast with blank pipe tobacco with the pipe tobacco that adds Ucar 35, to above-mentioned five carbon or six carbon monose Geraniol carbonic acid di-esters compounds (I~XIV) the humectation effect of pipe tobacco has been carried out the experiment contrast.Aqueous ethanolic solution with 50% is a solvent, and above-claimed cpd and Ucar 35 are mixed with solution and evenly spray in the blank pipe tobacco (addition be pipe tobacco weight 0.4%) respectively, sprays into the solvent of equivalent in the blank pipe tobacco.After each tobacco sample behind the application of sample being placed the climatic chamber balance 48h of 22 ℃ of relative humidity 60%, temperature; Every kind of pipe tobacco is got 4 increments; Every part of 10g; 2 parts of parallel appearance wherein are positioned in the encloses container of 22 ℃ of relative humidity 45%, temperature, two parts of parallel appearance are positioned in the encloses container of 22 ℃ of relative humidity 85%, temperature in addition; Every 24h weighs 1 time, surveys periodic water ratio according to calculating each part pipe tobacco with the weight differential of initial weight and initial aqueous rate; Measure the average that the result gets 2 parallel appearance, and make the time dependent curve of water ratio; Measure the dehydration always continue to each part pipe tobacco or suction and reach in a basic balancely, the result sees table 1 (" RH " representative " relative humidity " in the table).
Table 1 humectation and moistureproof test result
Test result shows; Under the condition of 22 ℃ of relative humidity 45%, temperature; The equilibrium moisture content of above-mentioned Geraniol carbonic acid di-esters compound is higher than Ucar 35 contrast pipe tobacco or blank pipe tobacco in various degree; And under the condition of 22 ℃ of relative humidity 85%, temperature; The equilibrium moisture content of above-mentioned monose ester compound is lower than Ucar 35 contrast pipe tobacco or blank pipe tobacco in various degree, shows that disclosed five carbon of the present invention or six carbon monose Geraniol carbonic acid di-esters compounds have humectation preferably and moisture-proof role to pipe tobacco.
Embodiment 18: slowly-releasing spices effect test
Tobacco sample to add Ucar 35 is contrast, to above-mentioned five carbon or six carbon monose Geraniol carbonic acid di-esters compounds (I~XIV) the slowly-releasing spices effect of pipe tobacco has been carried out the experiment contrast.After above-mentioned monose ester compound solution and propylene glycol solution being sprayed in the pipe tobacco (addition be pipe tobacco weight 0.4%) respectively and placing certain hour, 0.5 gram of taking a sample respectively is that solvent carries out supersound extraction with the methylene dichloride; Dichloromethane solution after the extraction utilizes the content of flavor matter in the gas chromatograph-mass spectrometer analysis filtrating behind filtering with microporous membrane.
Test result shows; The content of typical flavor matter all is higher than the tobacco sample that Ucar 35 was handled in various degree in the tobacco sample that above-mentioned monose ester compound was handled, and shows that disclosed five carbon of the present invention or six carbon monose Geraniol carbonic acid di-esters compounds have certain flavour ingredient evaporable effect in the pipe tobacco that slows down.
Embodiment 19: the thermo-cracking composition is analyzed
Adopt online thermal cracking-gas chromatograph-mass spectrometric hyphenated technique, (the thermo-cracking composition of I~XIV) is studied to above-mentioned five carbon or six carbon monose Geraniol carbonic acid di-esters compounds.Take by weighing about 0.2mg sample respectively, place solid sampler, under 200 ℃, 450 ℃ and 700 ℃, carry out the moment cracking, the cracking atmosphere is a helium, and split product is directly imported in the GCMS by helium and carries out qualitative analysis.
Mensuration result shows, these compounds all have aroma component such as Geraniol to produce at 200 ℃, 450 ℃ and 700 ℃, show that disclosed five carbon of the present invention or six carbon monose Geraniol carbonic acid di-esters compounds have the effect that thermo-cracking discharges aroma component.
Embodiment 20: the sensory evaluating smoking estimates
For disclosed five carbon of the present invention or six carbon monose Geraniol carbonic acid di-esters compound (I~XIV), carried out sensory evaluating smoking's evaluation with following method.
Aqueous ethanolic solution with 50% is a solvent; Above-claimed cpd and Ucar 35 are mixed with solution and evenly spray in the blank pipe tobacco (addition be pipe tobacco weight 0.4%) respectively; Each tobacco sample behind the application of sample is placed the climatic chamber balance 48h of 22 ℃ of relative humidity 60%, temperature; Process cigarette, put into balance 48h under the condition of 22 ℃ of relative humidity 60%, temperature again, it is carried out sensory evaluating smoking's evaluation by panel of experts.
Smoking result shows; Compare with Ucar 35 contrast cigarette; The cigarette flavor amount of having added above-mentioned monose ester compound increases, releases fragrant even, good with the fragrant Harmony of cigarette; The aesthetic quality be improved significantly, showing that disclosed five carbon of the present invention or six carbon monose Geraniol carbonic acid di-esters compounds have increases perfume quantity, releases the fragrant all even effect that improves the cigarette aesthetic quality.