CN101974041A - Five-carbon/five-carbon monosaccharide-L-menthoxyacetic acid diester compound and preparation method and application thereof - Google Patents
Five-carbon/five-carbon monosaccharide-L-menthoxyacetic acid diester compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a five-carbon/five-carbon monosaccharide-L-menthoxyacetic acid diester compound and a preparation method and application thereof and relates to a monosaccharide diester tobacco humectant. A novel five-carbon/six-carbon monosaccharide-L-menthoxyacetic acid diester compound shown in a formula (1) is prepared by a chemical synthesis method and the moisture preservation, damp resistance and incense slow releasing effects of the compound serving as the tobacco humectant are tested. A test result indicates that the monosaccharide-L-menthoxyacetic acid diester compound plays a role in preserving moisture, resisting damp and slowly releasing incense on tobacco and is a novel tobacco humectant with dual moisture preservation and incense slowly-releasing functions; and (1) in the formula (1), R represents a residue of five-carbon/six-carbon monosaccharide and two L-menthoxy acetyl can be positioned at any two possible positions of five-carbon/six-carbon monosaccharide.
Description
Technical field
The invention belongs to technical field of tobacco, relate to a class monose di-esters tobacco humectant, be specifically related to five carbon or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound, Preparation Method And The Use.
Background technology
Cigarette humectation performance and cigarette quality are in close relations, and flavouring humectation technical study is one of main direction of science and technology coming years research of China's tobacco industry and scientific and technical innovation.At present, the humectant that adopts in China's production of cigarettes is mainly polyhydroxy substances such as glycerine, propylene glycol, Xylitol, mainly relies on moisture in its absorbing environmental to keep pipe tobacco wetting and play the humectation effect, belongs to unidirectional humectant; Though this type of humectant can be kept the water ratio of pipe tobacco in the course of processing, improve the anti-processibility of pipe tobacco, it keeps the finished cigarettes water ratio and improves the effect of sucking comfort level really not satisfactory.In addition, because this type of poly-hydroxy class humectant does not have moisture-proof role, water ratio with tobacco that this type of humectant is handled is subjected to the influence of environment temperature, humidity bigger, promptly tobacco easily dries out and causes its dry sensation and pungency to strengthen in the exsiccant environment, and tobacco easily absorbs moisture and causes its moldy metamorphism in the warm environment of humidity.Therefore, research and develop novel having preserve moisture, moistureproof and the two-way or compound humectant of the fragrant effect of slowly-releasing material is arranged simultaneously, humectation performance and the international competitiveness that improves China's cigarette product had important practical significance.
Summary of the invention
The object of the present invention is to provide L-ethoxyacetic acid in the Meng di-esters compound of a kind of five carbon or six carbon monose compounds.
Second purpose of the present invention is to disclose the preparation method of such five carbon or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound.
The 3rd purpose of the present invention is to disclose the purposes of such five carbon or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound.
The object of the present invention is achieved like this:
A kind of five carbon or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound with following general formula,
Wherein, R represents the residue of five carbon monose or six carbon monose; In the dibasic acid esters molecule, two L-oxygen in Meng base ethanoyl are positioned at any two possible positions of five carbon or six carbon monose; 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, fructose, N.F,USP MANNITOL or sorbyl alcohol.
Second purpose of the present invention is achieved in that
The preparation method of a kind of five carbon as claimed in claim 1 or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound, be made up of steps A and step B:
X represents in the following formula: Cl, Br;
Steps A: with L-ethoxyacetic acid in the Meng is starting raw material, with the halogenating agent reaction, gets L-oxygen in Meng base acetyl halide under suitable solvent or condition of no solvent;
Step B: react with five carbon monose or derivatives thereofs or six carbon monose or derivatives thereofs in suitable solvent and under the acid binding agent existence condition by L-oxygen in the Meng base acetyl halide that steps A obtains, L-ethoxyacetic acid in the Meng dibasic acid esters and the polyesters mixture of five carbon or six carbon monose accordingly, through recrystallization or column chromatography purification, get corresponding monose-L-ethoxyacetic acid in Meng di-esters compound again.
Its concrete preparation method is described below:
Steps A: with L-ethoxyacetic acid in the Meng is starting raw material, with the halogenating agent reaction, gets L-oxygen in Meng base acetyl halide under suitable solvent or condition of no solvent;
Wherein, used halogenating agent is: chloro-formic ester (methyl-chloroformate, Vinyl chloroformate or superpalite etc.), phosphorus pentachloride, phosphorus trichloride, phosphorus tribromide, phosphorus oxychloride, thionyl chloride, oxalyl chloride, phosgene, two (trichloromethyl) carbonic ether, trichoroacetic chloride, 2,4,6-three chloro-1,3,5-s-triazine, benzene sulfonyl chloride, Tosyl chloride, methane sulfonyl chloride, dichloromethyl ether, Propylene oxide hexafluoride or a-halo enamine (
a-chloro-
N, N, 2-trimethylammonium allylamine or
a-bromo-
N, N, 2-trimethylammonium allylamines etc.), preferred halogenating agent is: phosphorus trichloride, thionyl chloride, two (trichloromethyl) carbonic ether,
a-chloro-
N, N, 2-trimethylammonium allylamine or
a-bromo-
N, N, 2-trimethylammonium allylamine;
Have that solvent for use is under the solvent condition: ether solvent (ether, isopropyl ether or methyl tertiary butyl ether), sherwood oil, tetrahydrofuran (THF),
N,
N-dimethyl formamide,
N-methyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), halohydrocarbon (methylene dichloride, chloroform, 1,2-ethylene dichloride or orthodichlorobenzene), aliphatic hydrocarbon (hexane, heptane or octane), C
3～C
8Aliphatic ketone, benzene, toluene, ethyl acetate, isopropyl acetate or acetonitrile, preferred solvent is: methylene dichloride, chloroform or ethyl acetate;
The molar feed ratio of L-ethoxyacetic acid in the Meng and halogenating agent is 1.0 ﹕ 1.0～6.0, and preferred molar feed ratio is 1.0 ﹕ 1.0～3.0; Temperature of reaction is 0 ℃～100 ℃, and preferable reaction temperature is 20 ℃～70 ℃; Reaction times is 0.5～48 hour, and the preferred reaction time is 1～20 hour.
Step B: react with five carbon monose or derivatives thereofs or six carbon monose or derivatives thereofs in suitable solvent and under the acid binding agent existence condition by L-oxygen in the Meng base acetyl halide that steps A obtains, L-ethoxyacetic acid in the Meng dibasic acid esters and the polyesters mixture of five carbon or six carbon monose accordingly, through recrystallization or column chromatography purification, get corresponding monose-L-ethoxyacetic acid in Meng di-esters compound again;
Wherein, the reaction solvent for use is: ether solvent (ether, isopropyl ether or methyl tertiary butyl ether), sherwood oil, normal heptane, tetrahydrofuran (THF),
N,
N-dimethyl formamide,
N-methyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), water, ethyl acetate, isopropyl acetate, methylene dichloride, chloroform, C
3～C
8Aliphatic ketone, benzene, toluene or pyridine, preferred solvent be tetrahydrofuran (THF),
N,
N-dimethyl formamide, methylene dichloride, ethyl acetate or pyridine;
Used acid binding agent is: trimethylamine class or quaternary ammonium bases (triethylamine, Tributylamine, trioctylamine, pyridine, N, N-dimethyl-a-phenylethylamine or 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 bicarbonate;
The molar feed ratio of L-oxygen in Meng base acetyl halide and five carbon monose or derivatives thereofs or six carbon monose or derivatives thereofs is 1.0～10.0 ﹕ 1.0, and preferred molar feed ratio is 2.0～4.0 ﹕ 1.0; The molar feed ratio of acid binding agent and L-oxygen in Meng base acetyl halide 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-10 ℃～40 ℃; Reaction times is 20 minutes～48 hours, and the preferred reaction time is 1～24 hour.
The 3rd purpose of the present invention is achieved in that
Five carbon disclosed in this invention or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound can be used as tobacco humectant; because this class wetting Agent for Printing Inks has certain water-soluble and fat-soluble simultaneously; can stablize the cigarette water ratio by the bilayer protective membrane of being separated by, reach the effect of humectation, protection against the tide and slowly-releasing material perfume (or spice) at tobacco surface formation profit.
Compared with prior art, beneficial effect of the present invention is as follows:
1, five carbon disclosed in this invention or six carbon monose-L-ethoxyacetic acid in Meng di-esters tobacco humectant can have simultaneously by form the bilayer protective membrane that profit is separated by on tobacco surface and preserves moisture and moistureproof two kinds of effects; the tobacco of handling through this class humectant dries out very slow in the exsiccant climatope; and it is also very slow to absorb moisture in the climatope of humidity, can effectively slow down the variation of tobacco moisture with envrionment conditions.
2, five carbon disclosed in this invention or six carbon monose-L-ethoxyacetic acid in Meng di-esters tobacco humectant also can be separated by the bilayer protective membrane and the volatilization that significantly slow down flavour ingredient in the tobacco by the profit that forms on tobacco surface, thereby has the fragrant effect of certain slowly-releasing material.
3, five carbon disclosed in this invention or six carbon monose-own British plain spirits of L-ethoxyacetic acid in Meng di-esters tobacco humectant, but but thermo-cracking or degraded produce flavour ingredient in aspiration procedure, make the more comfortable harmony of fragrance of cigarette, and these flavour ingredients itself promptly are present in the tobacco, just content is lower, therefore, this class tobacco humectant free from extraneous odour disclosed in this invention is good with the consistency of tobacco.
4, compare with widely used propylene glycol or glycerine on the present tobacco industry, product toxicological harmless after five carbon disclosed in this invention or six carbon monose-L-ethoxyacetic acid in Meng di-esters tobacco humectant burning, safe in utilization, more help the security of sucking of tobacco, be easy to apply.
Embodiment
Can further describe the present invention by the following examples, yet scope of the present invention is not limited to following embodiment.One of skill in the art can understand, and under the prerequisite that does not deviate from the spirit and scope of the present invention, can carry out various variations and modification to the present invention.
Embodiment 1:
3, the preparation of 6-two-(L-oxygen in Meng base acetyl)-D-glucopyanosyl ester (Compound I):
In reaction flask, add L-ethoxyacetic acid in the Meng 25.72 g(0.12 mol successively), thionyl chloride 28.56 g(0.24 mol) and chloroform 200 ml, temperature rising reflux stirring reaction 2 h, after reaction finishes, remove solvent and excessive thionyl chloride under reduced pressure, resistates is dissolved among chloroform 100 ml, is added dropwise to the D-glucose methyl glucoside 9.7g(0.05 mol that is cooled to-5～0 ℃), triethylamine 20.2g(0.20 mol) and
N,
NIn-dimethyl formamide 100 ml the mixed solutions, stirring at room is reacted 15 h, after reaction finishes, solid is separated out in filtration, and filtrate decompression is steamed and desolventized, and resistates is dissolved in methylene dichloride 200 ml, add 20% aqueous hydrochloric acid, 40 ml, with saturated aqueous sodium carbonate 50 ml and saturated aqueous common salt 50 ml washing, the gained dichloromethane solution is through anhydrous Na successively for stirring at room 2 h, organic layer
2SO
4Drying is filtered, and removes methylene dichloride under reduced pressure, and resistates gets 3,6-two-(L-oxygen in Meng base acetyl)-D-glucopyanosyl ester 15.2 g, yield 53.0% through purification by silica gel column chromatography (elutriant is: Lv Fang ﹕ methyl alcohol=15 ﹕ 1); HR-TOFMS (+Q)
M/z: 573.3636 ([C
30H
52O
10+ H]
+Calculated value: 573.3639).
Embodiment 2:
2, the preparation of 3-two-(L-oxygen in Meng base acetyl)-D-glucopyanosyl ester (Compound I I):
Operating process just substitutes thionyl chloride with embodiment 1 with phosphorus trichloride, triethylamine substitutes with pyridine,
N,
N-dimethyl formamide substitutes with ethyl acetate, and D-glucose methyl glucoside is with 4, and 6-O-isopropylidene-D-glucose methyl glucoside substitutes, and gets 2,3-two-(L-oxygen in Meng base acetyl)-D-glucopyanosyl ester, yield 56.0%; HR-TOFMS (+Q)
M/z: 573.3646 ([C
30H
52O
10+ H]
+Calculated value: 573.3639).
Embodiment 3:
2, the preparation of 3-two-(L-oxygen in Meng base acetyl)-D-gala pyrans sugar ester (compound III):
Operating process is just used thionyl chloride with embodiment 1
a-chloro-
N, N, 2-trimethylammonium allylamine substitutes, and triethylamine substitutes with pyridine,
N,
N-dimethyl formamide substitutes with tetrahydrofuran (THF), and D-glucose methyl glucoside is with 4, and 6-O-isopropylidene-D-semi-lactosi methyl glucoside substitutes, and gets 2,3-two-(L-oxygen in Meng base acetyl)-D-gala pyrans sugar ester, yield 63.0%; HR-TOFMS (+Q)
M/z: 573.3643 ([C
30H
52O
10+ H]
+Calculated value: 573.3639).
Embodiment 4:
2, the preparation of 6-two-(L-oxygen in Meng base acetyl)-D-gala pyrans sugar ester (compound IV):
Operating process is just used thionyl chloride with embodiment 1
a-chloro-
N, N, 2-trimethylammonium allylamine substitutes, and triethylamine substitutes with pyridine,
N,
N-dimethyl formamide substitutes with tetrahydrofuran (THF), and D-glucose methyl glucoside is with 3, and 4-O-isopropylidene-D-semi-lactosi methyl glucoside substitutes, and gets 2,6-two-(L-oxygen in Meng base acetyl)-D-gala pyrans sugar ester, yield 72.8%; HR-TOFMS (+Q)
M/z: 573.3633 ([C
30H
52O
10+ H]
+Calculated value: 573.3639).
Embodiment 5:
2, the preparation of 3-two-(L-oxygen in Meng base acetyl)-D-mannopyranose ester (compound V):
Operating process is with embodiment 3, and just with 4,6-O-isopropylidene-D-semi-lactosi methyl glucoside is with 4, and 6-O-isopropylidene-D-seminose methyl glucoside substitutes, and gets 2,3-two-(L-oxygen in Meng base acetyl)-D-mannopyranose ester, yield 71.0%; HR-TOFMS (+Q)
M/z: 573.3637 ([C
30H
52O
10+ H]
+Calculated value: 573.3639).
Embodiment 6:
4, the preparation of 6-two-(L-oxygen in Meng base acetyl)-D-mannopyranose ester (compound VI)
Operating process is with embodiment 3, and just with 4,6-O-isopropylidene-D-semi-lactosi methyl glucoside is with 2, and 3-O-isopropylidene-D-seminose methyl glucoside substitutes, and gets 4,6-two-(L-oxygen in Meng base acetyl)-D-mannopyranose ester, yield 74.0%; HR-TOFMS (+Q)
M/z: 573.3630 ([C
30H
52O
10+ H]
+Calculated value: 573.3639).
Embodiment 7:
1, the preparation of 6-two-(L-oxygen in Meng base acetyl)-D-sorb furans sugar ester (compound VI I)
Operating process is just used thionyl chloride with embodiment 1
a-chloro-
N, N, 2-trimethylammonium allylamine substitutes,
N,
N-dimethyl formamide substitutes with pyridine, and D-glucose methyl glucoside substitutes with the D-sorbose, gets 1,6-two-(L-oxygen in Meng base acetyl)-D-sorb furans sugar ester, yield 61.7%; HR-TOFMS (+Q)
M/z: 573.3646 ([C
30H
52O
10+ H]
+Calculated value: 573.3639).
Embodiment 8:
1, the preparation of 6-two-(L-oxygen in Meng base acetyl)-D-fruit furans sugar ester (compound VIII):
Operating process just substitutes the D-sorbose with embodiment 7 with D-fructose, get 1,6-two-(L-oxygen in Meng base acetyl)-D-fruit furans sugar ester, yield 66.5%; HR-TOFMS (+Q)
M/z: 573.3642 ([C
30H
52O
10+ H]
+Calculated value: 573.3639).
Embodiment 9:
1, the preparation of 6-two-(L-oxygen in Meng base acetyl)-Nitranitol (Compound I X):
Operating process just substitutes D-glucose methyl glucoside with embodiment 1 with N.F,USP MANNITOL, get 1,6-two-(L-oxygen in Meng base acetyl)-Nitranitol, yield 61.0%; HR-TOFMS (+Q)
M/z: 575.3790 ([C
30H
54O
10+ H]
+Calculated value: 575.3795).
Embodiment 10:
1, the preparation of 6-two-(L-oxygen in Meng base acetyl)-sorbitol ester (compounds X):
Operating process just substitutes D-glucose methyl glucoside with embodiment 1 with sorbyl alcohol, get 1,6-two-(L-oxygen in Meng base acetyl)-sorbitol ester, yield 62.0%; HR-TOFMS (+Q)
M/z: 575.3797 ([C
30H
54O
10+ H]
+Calculated value: 575.3795).
Embodiment 11:
3, the preparation of 5-two-(L-oxygen in Meng base acetyl)-D-wood furans sugar ester (compounds X I):
Operating process just substitutes D-glucose methyl glucoside with embodiment 1 with D-wood furanose methyl glucoside, get 3,5-two-(L-oxygen in Meng base acetyl)-D-wood furans sugar ester, yield 71.0%; HR-TOFMS (+Q)
M/z: 543.3530 ([C
29H
50O
9+ H]
+Calculated value: 543.3533).
Embodiment 12:
3, the preparation of 5-two-(L-oxygen in Meng base acetyl)-D-nuclear furans sugar ester (compounds X II):
Operating process just substitutes D-wood furanose methyl glucoside with embodiment 11 with D-nuclear furanose methyl glucoside, get 3,5-two-(L-oxygen in Meng base acetyl)-D-nuclear furans sugar ester, yield 67.5%; HR-TOFMS (+Q)
M/z: 543.3538 ([C
29H
50O
9+ H]
+Calculated value: 543.3533).
Embodiment 13:
3, the preparation of 5-two-(L-oxygen in Meng base acetyl)-D-arbinofuranose ester (compounds X III):
Operating process just substitutes D-wood furanose methyl glucoside with embodiment 11 with D-arbinofuranose methyl glucoside, get 3,5-two-(L-oxygen in Meng base acetyl)-D-arbinofuranose ester, yield 68.5%; HR-TOFMS (+Q)
M/z: 543.3527 ([C
29H
50O
9+ H]
+Calculated value: 543.3533).
Embodiment 14:
3, the preparation of 5-two-(L-oxygen in Meng base acetyl)-D-lysol furans sugar ester (compounds X IV):
Operating process just substitutes D-wood furanose methyl glucoside with embodiment 11 with D-lysol furanose methyl glucoside, get 3,5-two-(L-oxygen in Meng base acetyl)-D-lysol furans sugar ester, yield 69.0%; HR-TOFMS (+Q)
M/z: 543.3529 ([C
29H
50O
9+ H]
+Calculated value: 543.3533).
Embodiment 15:
1, the preparation of 5-two-(L-oxygen in Meng base acetyl)-D-ribulose ester (compounds X V):
Operating process just substitutes D-wood furanose methyl glucoside with embodiment 11 with the D-ribulose, get 1,5-two-(L-oxygen in Meng base acetyl)-D-ribulose ester, yield 70.0%; HR-TOFMS (+Q)
M/z: 543.3538 ([C
29H
50O
9+ H]
+Calculated value: 543.3533).
Embodiment 16:
1, the preparation of 5-two-(L-oxygen in Meng base acetyl)-D-xylulose ester (compounds X VI)
Operating process just substitutes D-wood furanose methyl glucoside with embodiment 11 with the D-xylulose, get 1,5-two-(L-oxygen in Meng base acetyl)-D-xylulose ester, yield 67.0%; HR-TOFMS (+Q)
M/z: 543.3527 ([C
29H
50O
9+ H]
+Calculated value: 543.3533).
Embodiment 17:
The effect test of humectation, protection against the tide and slowly-releasing material perfume (or spice):
For five carbon disclosed in this invention or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound (Compound I ~ XVI), estimate the fragrant effect of its humectation, protection against the tide and slowly-releasing material with the following method.
(1) humectation and moisture-proof role test
Tobacco sample with the adding propylene glycol is contrast, to above-mentioned five carbon or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound (Compound I ~ XVI) the humectation effect of pipe tobacco has been carried out the experiment contrast.Propylene glycol and above-mentioned monose di-esters compound solution are added respectively in the pipe tobacco (consumption of humectant be pipe tobacco weight 0.05～1%); Tobacco sample after will handling then places four climatic chambers (four conditions are respectively: 10 ℃ of temperature and relative humidity 40%, 30 ℃ of temperature and relative humidity 40%, 10 ℃ of temperature and relative humidity 80%, 30 ℃ of temperature and relative humidity 80%) that condition is different respectively, every 24h weighs 1 time, weigh altogether 6 times, calculate the water ratio of pipe tobacco respectively.
Test result shows, (Compound I ~ XVI) all has humectation and moisture-proof role in various degree to five carbon or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound, and its effect is better than the propylene glycol control group.
(2) the fragrant effect test of slowly-releasing material
Tobacco sample with the adding propylene glycol is contrast, to above-mentioned five carbon or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound (Compound I ~ XVI) the fragrant effect of slowly-releasing material of pipe tobacco has been carried out the experiment contrast.Propylene glycol and above-mentioned monose di-esters compound solution are added respectively in the pipe tobacco (consumption of humectant be pipe tobacco weight 0.05～1%); After various tobacco sample were all placed certain hour, each 0.5 gram of sampling was that solvent carries out supersound extraction with the methylene dichloride respectively; Dichloromethane solution after the extraction utilizes gas chromatograph-mass spectrometer to analyze the content of flavor matter in the filtrate behind filtering with microporous membrane.
Test result shows, the content of typical flavor matter all is higher than the tobacco sample that propylene glycol was handled to some extent in the tobacco sample that above-mentioned monose di-esters compound treatment is crossed, and shows that five carbon disclosed in this invention or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound has certain flavour ingredient evaporable effect in the pipe tobacco that slows down.
Claims (10)
1. five carbon or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound with following general formula,
Wherein, R represents the residue of five carbon monose or six carbon monose; In the dibasic acid esters molecule, two L-oxygen in Meng base ethanoyl are positioned at any two possible positions of five carbon or six carbon monose; 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, fructose, N.F,USP MANNITOL or sorbyl alcohol.
2. the preparation method of five carbon as claimed in claim 1 or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound is characterized in that, is made up of steps A and step B:
X represents in the following formula: Cl, Br;
Steps A: with L-ethoxyacetic acid in the Meng is starting raw material, with the halogenating agent reaction, gets L-oxygen in Meng base acetyl halide under suitable solvent or condition of no solvent;
Step B: react with five carbon monose or derivatives thereofs or six carbon monose or derivatives thereofs in suitable solvent and under the acid binding agent existence condition by L-oxygen in the Meng base acetyl halide that steps A obtains, L-ethoxyacetic acid in the Meng dibasic acid esters and the polyesters mixture of five carbon or six carbon monose accordingly, through recrystallization or column chromatography purification, get corresponding monose-L-ethoxyacetic acid in Meng di-esters compound again;
Among the above-mentioned steps A, solvent for use is: ether solvent, sherwood oil, tetrahydrofuran (THF),
N,
N-dimethyl formamide,
N-methyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), halohydrocarbon, aliphatic hydrocarbon, C
3~ C
8Aliphatic ketone, benzene, toluene, ethyl acetate, isopropyl acetate or acetonitrile;
Among the above-mentioned steps A, used halogenating agent is: chloro-formic ester, phosphorus pentachloride, phosphorus trichloride, phosphorus tribromide, phosphorus oxychloride, thionyl chloride, oxalyl chloride, phosgene, two (trichloromethyl) carbonic ether, trichoroacetic chloride, 2,4,6-three chloro-1,3,5-s-triazine, benzene sulfonyl chloride, Tosyl chloride, methane sulfonyl chloride, dichloromethyl ether, Propylene oxide hexafluoride or a-halo enamine;
Among the above-mentioned steps B, the reaction solvent for use is: ether solvent, sherwood oil, normal heptane, tetrahydrofuran (THF),
N,
N-dimethyl formamide,
N-methyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), water, ethyl acetate, isopropyl acetate, methylene dichloride, chloroform, C
3～C
8Aliphatic ketone, benzene, toluene or pyridine;
Among the above-mentioned steps B, used acid binding agent is: trimethylamine class or quaternary ammonium bases, basic metal or alkaline earth metal hydroxides, basic metal or alkaline earth metal carbonate, basic metal or alkali metal bicarbonates.
3. according to the preparation method of described five carbon of claim 2 or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound, it is characterized in that solvent for use is preferably in the described steps A: methylene dichloride, chloroform or ethyl acetate.
4. according to the preparation method of described five carbon of claim 2 or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound, it is characterized in that used halogenating agent is preferably in the described steps A: phosphorus trichloride, thionyl chloride, two (trichloromethyl) carbonic ether,
a-chloro-
N, N, 2-trimethylammonium allylamine or
a-bromo-
N, N, 2-trimethylammonium allylamine.
5. according to the preparation method of described five carbon of claim 2 or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound, it is characterized in that solvent for use is preferably among the described step B: tetrahydrofuran (THF),
N,
N-dimethyl formamide, methylene dichloride, ethyl acetate or pyridine.
6. according to the preparation method of described five carbon of claim 2 or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound, it is characterized in that used acid binding agent is preferably among the described step B: triethylamine, pyridine or sodium bicarbonate.
7. according to the preparation method of described five carbon of claim 2 or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound, it is characterized in that: in the steps A, the molar feed ratio of L-ethoxyacetic acid in the Meng and halogenating agent is 1.0 ﹕ 1.0～6.0, temperature of reaction is 0 ℃～100 ℃, and the reaction times is 0.5～48 hour; Among the step B, the molar feed ratio of L-oxygen in Meng base acetyl halide and five carbon monose or five carbon monosaccharide derivatives or six carbon monose or six carbon monosaccharide derivatives is 1.0～10.0 ﹕ 1.0, the molar feed ratio of acid binding agent and L-oxygen in Meng base acetyl halide is 1.0～10.0 ﹕ 1.0, temperature of reaction is-40 ℃～120 ℃, and the reaction times is 20 minutes～48 hours.
8. according to the preparation method of described five carbon of claim 7 or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound, it is characterized in that, in the steps A, the molar feed ratio of L-ethoxyacetic acid in the Meng and halogenating agent is preferably 1.0 ﹕ 1.0～3.0, temperature of reaction is preferably 20 ℃～70 ℃, and the reaction times is preferably 1～20 hour.
9. according to the preparation method of described five carbon of claim 7 or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound, it is characterized in that, among the step B, the molar feed ratio of L-oxygen in Meng base acetyl halide and five carbon monose or five carbon monosaccharide derivatives or six carbon monose or six carbon monosaccharide derivatives is preferably 2.0～4.0 ﹕ 1.0; The molar feed ratio of acid binding agent and L-ethoxyacetic acid in the Meng is preferably 1.0～3.0 ﹕ 1.0, and temperature of reaction is preferably-10 ℃～40 reaction times and is preferably 1～24 hour.
10. five carbon as claimed in claim 1 or six carbon monose-L-ethoxyacetic acid in Meng di-esters compound are as the application of tobacco humectant.
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Cited By (5)
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| CN102286034A (en) * | 2011-09-05 | 2011-12-21 | 川渝中烟工业公司 | Monosaccharide alpha-ionol carbonic acid di-ester compound as well as preparation method and application thereof |
| CN102286035A (en) * | 2011-09-05 | 2011-12-21 | 川渝中烟工业公司 | Bimenthoxycarbonylmonose ester compound as well as preparation method and application thereof |
| CN102304155A (en) * | 2011-09-05 | 2012-01-04 | 川渝中烟工业公司 | Monosaccharide geraniol carbonate diester compound, preparation method and use thereof |
| CN102311464A (en) * | 2011-09-05 | 2012-01-11 | 川渝中烟工业公司 | Monomenthyloxycarbonyl monosugar ester compounds, preparation method thereof and purpose thereof |
| CN102311465A (en) * | 2011-09-05 | 2012-01-11 | 川渝中烟工业公司 | Monosaccharide geraniol carbonate monoester compound and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102286034A (en) * | 2011-09-05 | 2011-12-21 | 川渝中烟工业公司 | Monosaccharide alpha-ionol carbonic acid di-ester compound as well as preparation method and application thereof |
| CN102286035A (en) * | 2011-09-05 | 2011-12-21 | 川渝中烟工业公司 | Bimenthoxycarbonylmonose ester compound as well as preparation method and application thereof |
| CN102304155A (en) * | 2011-09-05 | 2012-01-04 | 川渝中烟工业公司 | Monosaccharide geraniol carbonate diester compound, preparation method and use thereof |
| CN102311464A (en) * | 2011-09-05 | 2012-01-11 | 川渝中烟工业公司 | Monomenthyloxycarbonyl monosugar ester compounds, preparation method thereof and purpose thereof |
| CN102311465A (en) * | 2011-09-05 | 2012-01-11 | 川渝中烟工业公司 | Monosaccharide geraniol carbonate monoester compound and preparation method and application thereof |
| CN102304155B (en) * | 2011-09-05 | 2014-01-15 | 川渝中烟工业有限责任公司 | Monosaccharide geraniol carbonate diester compound, preparation method and use thereof |
| CN102311465B (en) * | 2011-09-05 | 2014-02-26 | 川渝中烟工业有限责任公司 | Monosaccharide geraniol carbonate monoester compound and preparation method and application thereof |
| CN102311464B (en) * | 2011-09-05 | 2014-03-26 | 川渝中烟工业有限责任公司 | Monomenthyloxycarbonyl monosugar ester compounds, preparation method thereof and purpose thereof |
| CN102286034B (en) * | 2011-09-05 | 2014-05-07 | 川渝中烟工业有限责任公司 | Monosaccharide alpha-ionol carbonic acid di-ester compound as well as preparation method and application thereof |
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Address after: 610017 Jackie Chan Road, Chengdu economic and Technological Development Zone, Longquanyi District, Sichuan, China, No. 2, No. Applicant after: China Tobacco Chuanyu Industrial Co., Ltd. Address before: 610017 Jackie Chan Road, Chengdu economic and Technological Development Zone, Longquanyi District, Sichuan, China, No. 2, No. Applicant before: China Tobacco Chuanyu Industrial Corporation |
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