CN105669612B - A kind of methyl 2 of 3 hydroxyl 4（5 hydrogen）The preparation method of furanone - Google Patents
A kind of methyl 2 of 3 hydroxyl 4（5 hydrogen）The preparation method of furanone Download PDFInfo
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- CN105669612B CN105669612B CN201610126494.7A CN201610126494A CN105669612B CN 105669612 B CN105669612 B CN 105669612B CN 201610126494 A CN201610126494 A CN 201610126494A CN 105669612 B CN105669612 B CN 105669612B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
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Abstract
The present invention relates to a kind of methyl 2 of 3 hydroxyl 4（5 hydrogen）The simple and convenient process for preparing of furanone, after it mixes xylose and lysine with water, in 60-100 DEG C of heating response 0.5-4h, reaction solution is extracted with ethyl acetate after terminating in reaction, and organic phase is purified to obtain the methyl 2 of 3 hydroxyl 4（5 hydrogen）Furanone.Using the secure and cheap xylose being easy to get and lysine as raw material in the inventive method, cost is greatlyd save；Catalyst need not be additionally added, and synthesis step is easy, is to obtain the methyl 2 of 3 hydroxyl of target product 4 merely through single step reaction（5 hydrogen）Furanone, it is to avoid the deficiencies in the prior art, is the methyl 2 of 3 hydroxyl 4（5 hydrogen）The preparation of furanone provides a new approach.
Description
Technical field
The invention belongs to chemosynthesis technical field, and in particular to a kind of 3- hydroxy-4-methyls -2（5 hydrogen）- furanone
Simple and convenient process for preparing.
Background technology
3- hydroxy-4-methyls -2（5 hydrogen）- furanone is a kind of insect attractant, can be used to trap housefly and cockroach, generally
It is also used for 4- methyl -3- (1- pyrrolidinyl) -2 (5H)-furanone of the synthesis with cooling sensation.On 3- hydroxyl -4- first
Base -2（5 hydrogen）The synthetic method of-furanone, document Tetrahedron: Asymmetry.2004. Vol.15(4).593-
601. provide a kind of reaction scheme：
；
The reaction scheme reactions steps are more, and route is long, post-reaction treatment complex steps, some raw materials and reagent toxicity compared with
Greatly, the application of the route is limited；If being reacted since second step or the 3rd step, the acquisition of some raw materials becomes more again
It is difficult.
Journal of Agricultural and Food Chemistry (2001), 49(11), 5383-5390
The synthetic route of middle offer is as follows：
；
The reaction scheme raw material is inflammable or poisonous, limits the application of the route.
The synthetic route provided in Chemistry Letters (1991), (8), 1349-50. is as follows：
；
The material toxicity that the reaction scheme has is larger, the more difficult acquisition having, and limits the application of the route.
The content of the invention
Present invention aims to overcome that there is provided a kind of 3- hydroxy-4-methyls -2 for prior art defect（5 hydrogen）- furanone
Simple and convenient process for preparing.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of 3- hydroxy-4-methyls -2（5 hydrogen）The simple and convenient process for preparing of-furanone, it mixes xylose and lysine with water
After conjunction, in 60-100 DEG C of heating response 0.5-4h, reaction solution is extracted with ethyl acetate in reaction after terminating, and organic phase is purified to be obtained
To 3- hydroxy-4-methyls -2（5 hydrogen）- furanone；Specific synthetic route is as follows：
。
Specifically, the mass ratio of xylose and lysine is preferably 1：1~6.In the inventive method, ethyl acetate can also be with
Raw material xylose, lysine and water are mixed together, but heating response temperature need to be controlled to be no more than 70 DEG C, after reaction terminates, and are stood
Layering, direct purification organic phase.
The organic phase is reclaimed after ethyl acetate, is purified using column chromatography, is specially：Silica gel dress post, loading, use exhibition
Agent elution silicagel column is opened, leacheate is detected with TLC, will contain 3- hydroxy-4-methyls -2（5 hydrogen）The elution of-furanone
3- hydroxy-4-methyls -2 are obtained after liquid merging, concentration（5 hydrogen）- furanone.
In column chromatography purge process, the mass ratio of organic phase and silica gel is preferably 1：50~60, solvent is preferably by volume
Than for 1：2~6 petroleum ether and ethyl acetate composition.
Compared to the prior art, the beneficial effect of the inventive method：
1）Using the secure and cheap xylose being easy to get and lysine as raw material, to greatly save cost in the inventive method；
Catalyst need not be additionally added, and synthesis step is easy, is to obtain target product 3- hydroxyl -4- first merely through single step reaction
Base -2（5 hydrogen）- furanone；
2）The synthesis condition of preparation method of the present invention is gentle, and range of reaction temperature is relatively wide, is easily controlled, it is to avoid existing
There is the deficiency of technology, be 3- hydroxy-4-methyls -2（5 hydrogen）The preparation of-furanone provides a new approach.
Brief description of the drawings
Fig. 1 is the gained 3- hydroxy-4-methyls -2 of embodiment 1（5 hydrogen）The GC detection spectrograms of-furanone product（Chromatogram
Instrument：Agilent 7820A；Chromatographic column：Agilent 19091N-133（30.0 mm×0.25 mm×0.25 μm）；Injection port
Temperature：260℃；Temperature programming：35 DEG C of 5 min of holding of initial temperature, are warming up to 240 DEG C with 5 DEG C/min, keep 20 min；Detector：
Hydrogen flame detector；Sample size：1 μL；Carrier gas：High Purity Nitrogen, the mL/min of flow 1；Split ratio 20:1）；It can be seen from the figure that：
Under this chromatographic condition, product retention time is 34min, and without obvious impurity peaks, purity is higher；
Fig. 2 is the gained 3- hydroxy-4-methyls -2 of embodiment 1（5 hydrogen）The high resolution mass spectrum figure of-furanone product；High score
It is 114 to distinguish that mass spectrogram provides molecular weight of product, and chemical formula is C5H6O3；
Fig. 3 is the gained 3- hydroxy-4-methyls -2 of embodiment 1（5 hydrogen）The infrared spectrum of-furanone product；3192 in figure
cm-1Place should be hydroxyl signal, 2956 cm-1For the hydrocarbon stretching vibration frequency of saturated carbon, 1699 cm-1Place is probably in the presence of altogether
The carbonyl absorption signal of yoke effect, 1641 cm-1There is carbon-carbon double bond, 1368cm in the signal instruction at place-1With 1459 cm-1It should be
Methyl signals, 1300-1050 cm-1There is C-O absorption signals；
Fig. 4 is the gained 3- hydroxy-4-methyls -2 of embodiment 1（5 hydrogen）The nucleus magnetic hydrogen spectrum figure of-furanone product；Can in figure
To find out：δ8.33（1H, s）Ppm proton is the hydroxyl proton of enol, δ 4.52（2H, s）Ppm proton is methylene matrix
Son, δ 2.13（3H, s）For methyl proton；
Fig. 5 is the gained 3- hydroxy-4-methyls -2 of embodiment 1（5 hydrogen）The nuclear-magnetism carbon spectrogram of-furanone product.Can be with figure
Find out that 13C nuclear-magnetisms are composed（100 MHz, d, ppm）：δ 195.4ppm are carbonyl carbon, and the ppm of δ 173.0 are the double key carbon of connection hydroxyl,
The ppm of δ 134.5 are the double key carbon of connection methyl, and the ppm of δ 72.5 are mesomethylene carbon, and the ppm of δ 13,12 are methyl carbon.
Embodiment
Technical scheme is further discussed in detail with reference to embodiments, but protection scope of the present invention
It is not limited thereto.
Embodiment 1
A kind of 3- hydroxy-4-methyls -2（5 hydrogen）The simple and convenient process for preparing of-furanone, be specially：
100g xyloses and 300g lysines are added in 1000ml water, in 95 DEG C of heating stirring reaction 1h, reaction terminates
After be down to room temperature, with 400mL ethyl acetate extractive reaction liquid, after organic phase recycling design ethyl acetate, upper silicagel column uses body
Product is than being 1:4 petroleum ether and ethyl acetate mixtures elutes silicagel column as solvent, and leacheate is detected with TLC,
3- hydroxy-4-methyls -2 will be contained（5 hydrogen）The leacheate of-furanone merges, after concentration 3- hydroxy-4-methyls -2（5 hydrogen）- furan
Mutter ketone finished product 11.5g, yield 15.13%, purity >=98%.
Embodiment 2
A kind of 3- hydroxy-4-methyls -2（5 hydrogen）The simple and convenient process for preparing of-furanone, be specially：
100g xyloses and 300g lysines are added in 1000ml water and 400mL ethyl acetate, in 70 DEG C of heating stirrings
3h is reacted, reaction is down to room temperature after terminating, taken after ethyl acetate phase, recycling design ethyl acetate, upper silicagel column uses volume ratio
For 1:4 petroleum ether and ethyl acetate mixtures elutes silicagel column as solvent, and leacheate is detected with TLC, will be contained
There are 3- hydroxy-4-methyls -2（5 hydrogen）The leacheate of-furanone merges, after concentration 3- hydroxy-4-methyls -2（5 hydrogen）- furanone
Finished product 7.9g, yield 10.39%, purity >=98%.
Claims (4)
1. a kind of 3- hydroxy-4-methyls -2（5 hydrogen）The preparation method of-furanone, it is characterised in that by xylose and lysine and water
After mixing, in 60-100 DEG C of heating response 0.5-4h, reaction solution is extracted with ethyl acetate after terminating in reaction, and organic phase is purified
Obtain 3- hydroxy-4-methyls -2（5 hydrogen）- furanone.
2. 3- hydroxy-4-methyls -2 as claimed in claim 1（5 hydrogen）The preparation method of-furanone, it is characterised in that xylose and
The mass ratio of lysine is 1：1~6.
3. 3- hydroxy-4-methyls -2 as claimed in claim 1（5 hydrogen）The preparation method of-furanone, it is characterised in that organic phase
Reclaim after ethyl acetate, purified using column chromatography, be specially：Silica gel dress post, loading, elute silicagel column with solvent, drench
Washing lotion is detected with TLC, will contain 3- hydroxy-4-methyls -2（5 hydrogen）The leacheate of-furanone merges, after concentration 3-
Hydroxy-4-methyl -2（5 hydrogen）- furanone.
4. 3- hydroxy-4-methyls -2 as claimed in claim 3（5 hydrogen）The preparation method of-furanone, it is characterised in that organic phase
Mass ratio with silica gel is 1：50~60, solvent is 1 by volume ratio：2~6 petroleum ether and ethyl acetate composition.
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| CN102093319B (en) * | 2010-11-22 | 2013-01-23 | 吉首大学 | 3-aryl-4-(2-glycosyl/amino ethyoxyl)-2(5H)-furanone compound, preparation method thereof and application thereof |
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