CN110272399A - The method of biomass-based furfuryl alcohol derivative green high-efficient synthesis Coumarin methane - Google Patents
The method of biomass-based furfuryl alcohol derivative green high-efficient synthesis Coumarin methane Download PDFInfo
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- CN110272399A CN110272399A CN201910635719.5A CN201910635719A CN110272399A CN 110272399 A CN110272399 A CN 110272399A CN 201910635719 A CN201910635719 A CN 201910635719A CN 110272399 A CN110272399 A CN 110272399A
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- furfuryl alcohol
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- 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
- C07D307/36—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 only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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Abstract
The invention discloses the methods of biomass-based furfuryl alcohol derivative green high-efficient synthesis Coumarin methane, successively biomass-based furfuryl alcohol derivative, additive, solvent are added in reaction vessel, reach after the reaction time is cooled to room temperature, then the derivative of Coumarin methane can be obtained in the organic phase of vacuum fractionation transfer, and product yield may be up to 82%.This method is very low to production equipment by under mild condition of normal pressure, meets green, efficiently, the principle of safety in production；The furfuryl alcohol derivative that no catalyst participates in the conversion of biomass base of green high-efficient is highly useful chemical products Coumarin methane, what raw material can be widely present from nature, it is obtained in the low biomass of manufacturing cost, the invention reaction condition is as mild as a dove, technological operation is very simple, and product is very easy to separation, and can realize recycling for solvent in the industrial production, it realizes the green high-efficient conversion of biomass resource, while also avoiding bring environmental problem in technical process.
Description
Technical field
The present invention relates to biomass transformation technology fields, and more specifically more particularly to biomass-based furfuryl alcohol derivative is green
The method that color efficiently synthesizes Coumarin methane.
Background technique
Currently, biomass as on the earth with great potentiality sustainable origin of organic carbon, production fuel, material and
It is the substitute of petroleum resources in the technical process of important chemical products, but in the conversion of chemicals derived from most of biology bases,
Some noble metal catalysts are usually used, acid, condition of high voltage etc., the environmental problem system of harsh reaction condition and reaction generation
About its large-scale application.Glucose and fructose are the most common hexoses of nature, downstream derivative 5 hydroxymethyl furfural, 5-
Methyl furfural, furfural are considered as very important biology base plateform molecules compound, furfuryl alcohol, and 5- methyl furfuryl alcohol can pass through chaff
Aldehyde, 5 methyl furfural, the selective reduction of 5 hydroxymethyl furfural hydrogenate to obtain, and are a kind of very common biomass-based furans
Derivative, because in the chemical products that its green high-efficient Synthesis is important are extremely important.
Industrial Coumarin methane Derivatives have conjunction reported in the literature there are no mature Industrialized synthesis method at present
At Coumarin methane Derivatives method mainly include the following types:
1. some is that a Fu Rui Deer-carat occurs under the action of an acid using the furans of furfuryl alcohol derivative and an other molecule
Husband's kind type reaction generates Coumarin methane Derivatives, such as trifluoroacetic acid (Chem. Eur., 2000,6,4091-4103),
Sulfuric acid (ChemSusChem., 2010,3,1158-1161), sulfonic acid analog (Green Chem., 2017,19,
4804-4810).
2. some is to use biomass-based furan derivatives and formaldehyde under the catalysis of acid, acetaldehyde, alkyl aldehydes etc. are gathered
Conjunction obtains Coumarin methane Derivatives, such as Villandier research group (Angew. Chem., Int. Ed., 2011,
50,2375-2378.), Linhua Song research group (Green Chem., 2014,16,1436-1443.).
3. some polymerize to form Coumarin methane Derivatives by using metallic catalyst catalysis furfuryl alcohol derivative, such as
Ramasastry research group uses ytterbium catalyst (Org. Biomol. Chem., 2013,11,8030- 8035.), U.
M. Dzhemilev research group has used rhodium catalyst (Russ. J. Appl. Chem., 2007,80,1687-
1690.).
It reacts all inevitable above and uses noble metal catalyst, corrosive acid etc., for this purpose, we have invented one
Kind without catalyst, reaction condition is mild, the method for preparing Coumarin methane of the green high-efficient of simple process.
Summary of the invention
The purpose of the present invention is to solve expensive catalyst present in the existing technology for preparing Coumarin methane Derivatives,
The disadvantages of acid corrosion, complex process, the present invention provide a kind of from biomass-based furfuryl alcohol derivative green high-efficient synthesis Coumarin
The method of methane Derivatives.
The present invention is achieved by the following technical solutions, and steps are as follows:
Successively biomass-based furfuryl alcohol derivative, additive, solvent are added in reaction vessel, reaching the reaction time is cooled to
After room temperature, then the derivative of Coumarin methane is can be obtained in the organic phase of vacuum fractionation transfer, and product yield may be up to 82%；
Reaction equation is as follows:
Preferably, the additive includes additive one and additive two, one mole of additive of biomass-based chaff 01 derivatives ︰
Than for 1-1000, most preferably 1-300；Biomass-based two molar ratio of chaff 01 derivatives ︰ additive is 1-1000, most preferably 1-
100；Biomass-based chaff 01 derivatives ︰ solvent molar ratio is 1-1000, most preferably 1-40；Additive Yi ︰ solvent molar ratio is
200-1, most preferably 2-1；Additive Er ︰ solvent molar ratio is 1-80；Reaction temperature is 25-200 DEG C, most preferably 80-140 DEG C；
Gas pressure is 1-100atm, most preferably 1-2atm；Reaction time is 0.01-24h, most preferably 1-8h.
Preferably, the biomass-based furfuryl alcohol derivative includes: furfuryl alcohol, 5- methyl furfuryl alcohol, 5- methylol furfuryl alcohol, and 2,5- bis-
Or mixtures thereof hydroxymethylfurans.
Preferably, the additive two includes: air, oxygen or a certain proportion of containing oxygen gas mixture.
Preferably, the solvent includes: hexamethylene, hexane, octane, toluene, paraxylene, mesitylene, acetic acid second
Ester, 1,2- dichloroethanes, methylene chloride, Isosorbide-5-Nitrae-dioxane, tetrahydrofuran, or mixtures thereof ether.
Technical effect and advantage of the invention:
1, biomass-based furfuryl alcohol derivative green high-efficient synthesizes Coumarin methane, and streamline operation avoids waste gas and waste liquid from bringing
Environmental problem, realize the efficient utilization of resource.
2, the present invention need to only carry out under lower temperature, condition of normal pressure, of less demanding to production equipment, meet safety in production
Principle.
3, the present invention does not need addition metallic catalyst or acid using common biomass-based furfuryl alcohol as raw material to be urged
Change, solvent can be recycled, and product is very easy to separation and obtains, and have very big potential industrial application.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not
For limiting the present invention.Based on the embodiments of the present invention, those of ordinary skill in the art are not before making creative work
Every other embodiment obtained is put, shall fall within the protection scope of the present invention.
Embodiment 1
19.6mg furfuryl alcohol, 0.5mL distilled water, 0.5mL hexamethylene, by reaction tube are sequentially added in 25mL Schlenk reaction tube
Sealing, which is placed on, is heated to 100 DEG C with stirring module, keeps 2h.Reaction tube is cooled to room temperature after reaction, is shifted organic
Mutually removing organic phase to obtain the yield of Coumarin methane using Rotary Evaporators is 15%, and product passes through nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon
Spectrum, Mass Spectrometer Method are confirmed.
The detection of Coumarin methane production and calculation basis following methods carry out:
The flask for receiving reaction organic phase weighs the quality m (empty bottle) of empty bottle before receiving organic phase, then has received
The flask of machine phase, which is taken away, removes organic phase using Rotary Evaporators, removes flask after removing organic phase, flask is connected vacuum pump
Decompression suction filtration, the quality m (total) of room temperature lower-weighing flask are carried out, the quality m (product) of product is equal to m (total) and subtracts m (empty bottle),
M (product) obtains the mole of product divided by the molecular weight of product, and the mole of product is divided by the mole of investment raw material divided by 2
The yield that can be obtained by reaction multiplied by 100%, then takes a small amount of product to carry out nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon spectrum, and mass spectrum is tested
Card.
Quantitative analysis using gas chromatograph Agilent 7820A series (fid detector, AgilentHP-5 chromatographic column:
30m*32um*0.25um).
Qualitative analysis uses gaseous mass analyzer ThermoscientificTRACE1310 (HP-5 capillary chromatograph 30m*320
μm*0.25μm)。
The calculation of yield formula of Coumarin methane；
Coumarin methane production=(Coumarin methane mole/(mole/2 of furfuryl alcohol derivative)) × 100%.
Embodiment 2
19.6mg furfuryl alcohol, 1.0 mL ultrapure waters are sequentially added in 25mL Schlenk reaction tube, 1.0mL hexamethylene will react
The seal of tube, which is placed on, is heated to 100 DEG C with stirring module, keeps 2h.Reaction tube is cooled to room temperature after reaction, transfer has
It is 16% that machine mutually removes organic phase to obtain the yield of Coumarin methane using Rotary Evaporators, and product passes through nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon
Spectrum, Mass Spectrometer Method are confirmed.
Embodiment 3
Sequentially add 19.6mg furfuryl alcohol and 22.5mg5- methyl furfuryl alcohol in 25mL Schlenk reaction tube, 1.0 mL distilled water,
The reaction seal of tube is placed on and is heated to 100 DEG C with stirring module, keeps 2h by 1.0mL toluene.It is after reaction that reaction tube is cold
But to room temperature, shifting organic phase and removing organic phase to obtain the yield of Coumarin methane using Rotary Evaporators is 13%, and product passes through
Nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon spectrum, Mass Spectrometer Method are confirmed.
Embodiment 4
Sequentially add 19.6mg furfuryl alcohol and 22.5mg5- methyl furfuryl alcohol in 25mL Schlenk reaction tube, 1.0mL distilled water,
The reaction seal of tube is placed on and is heated to 60 DEG C with stirring module, keeps 2h by 1.0mL 1,2- methylene chloride.After reaction will
Reaction tube is cooled to room temperature, and transfer organic phase removes organic phase using Rotary Evaporators and obtains the yield of asymmetric Coumarin methane
It is 15%, product passes through nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon spectrum, and Mass Spectrometer Method is confirmed.
Embodiment 5
19.6mg furfuryl alcohol, 1.0 mL distilled water are sequentially added in 25mL Schlenk reaction tube, 1.0mL hexamethylene will react
The seal of tube, which is placed on, is heated to 100 DEG C with stirring module, keeps 2h.Reaction tube is cooled to room temperature after reaction, transfer has
It is 16% that machine mutually removes organic phase to obtain the yield of Coumarin methane using Rotary Evaporators, and product passes through nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon
Spectrum, Mass Spectrometer Method are confirmed.
Embodiment 6
19.6mg furfuryl alcohol, 1.0 mL distilled water are sequentially added in 25mL Schlenk reaction tube, 1.0mL hexamethylene will react
The seal of tube, which is placed on, is heated to 140 DEG C with stirring module, keeps 2h.Reaction tube is cooled to room temperature after reaction, transfer has
It is 21% that machine mutually removes organic phase to obtain the yield of Coumarin methane using Rotary Evaporators, and product passes through nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon
Spectrum, Mass Spectrometer Method are confirmed.
Embodiment 7
19.6mg furfuryl alcohol, 1.0 mL distilled water are sequentially added in 25mL Schlenk reaction tube, 1.0mL hexamethylene will react
The seal of tube, which is placed on, is heated to 100 DEG C with stirring module, keeps 6h.Reaction tube is cooled to room temperature after reaction, transfer has
It is 16% that machine mutually removes organic phase to obtain the yield of Coumarin methane using Rotary Evaporators, and product passes through nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon
Spectrum, Mass Spectrometer Method are confirmed.
Embodiment 8
19.6mg furfuryl alcohol, 1.0 mL distilled water are sequentially added in 25mL Schlenk reaction tube, 1.0 mL hexamethylenes will react
The seal of tube, which is placed on, is heated to 140 DEG C with stirring module, keeps 8h.Reaction tube is cooled to room temperature after reaction, transfer has
It is 12% that machine mutually removes organic phase to obtain the yield of Coumarin methane using Rotary Evaporators, and product passes through nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon
Spectrum, Mass Spectrometer Method are confirmed.
Embodiment 9
19.6mg furfuryl alcohol, 50mL distilled water are sequentially added in 500mL round-bottomed flask, flask is placed on and has by 50 mL hexamethylenes
Stir 100 DEG C of oil bath condensate return 2h.Reaction tube is cooled to room temperature after reaction, transfer organic phase uses rotary evaporation
It is 21% that instrument, which removes organic phase and obtains the yield of Coumarin methane, and product passes through nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon spectrum, and Mass Spectrometer Method obtains
It confirms.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features,
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (9)
1. the method for biomass-based furfuryl alcohol derivative green high-efficient synthesis Coumarin methane, characterized by the following steps:
Successively biomass-based furfuryl alcohol derivative, additive, solvent are added in reaction vessel, reaching the reaction time is cooled to room temperature
Afterwards, the derivative of Coumarin methane can be obtained in the organic phase that then vacuum fractionation shifts, and product yield may be up to 82%.
2. the method for biomass-based furfuryl alcohol derivative green high-efficient synthesis Coumarin methane according to claim 1, special
Sign is: the additive includes additive one and additive two, and described biomass-based one mole of additive of chaff 01 derivatives ︰
Than for 1-1000, most preferably 1-300；Biomass-based two molar ratio of chaff 01 derivatives ︰ additive is 1-1000, most preferably 1-
100；Biomass-based chaff 01 derivatives ︰ solvent molar ratio is 1-1000, most preferably 1-40；Additive Yi ︰ solvent molar ratio is
200-1, most preferably 2-1；Additive Er ︰ solvent molar ratio is 1-80.
3. the method for biomass-based furfuryl alcohol derivative green high-efficient synthesis Coumarin methane according to claim 1, special
Sign is: the biomass-based furfuryl alcohol derivative includes: furfuryl alcohol, 5- methyl furfuryl alcohol, 5- methylol furfuryl alcohol, 2,5- dihydroxymethyl furans
Or mixtures thereof mutter.
4. the method for biomass-based furfuryl alcohol derivative green high-efficient synthesis Coumarin methane according to claim 1, special
Sign is: the reaction temperature is 25-200 DEG C, most preferably 80-140 DEG C.
5. the method for biomass-based furfuryl alcohol derivative green high-efficient synthesis Coumarin methane according to claim 1, special
Sign is: the gas pressure is 1-100atm, most preferably 1-2atm.
6. the method for biomass-based furfuryl alcohol derivative green high-efficient synthesis Coumarin methane according to claim 1, special
Sign is: the reaction time is 0.01-24h, most preferably 1-8h.
7. the method for biomass-based furfuryl alcohol derivative green high-efficient synthesis Coumarin methane according to claim 1, special
Sign is: the solvent includes: hexamethylene, hexane, octane, toluene, paraxylene, mesitylene, ethyl acetate, and 1,2- bis-
Chloroethanes, methylene chloride, Isosorbide-5-Nitrae-dioxane, tetrahydrofuran, or mixtures thereof ether.
8. the method for biomass-based furfuryl alcohol derivative green high-efficient synthesis Coumarin methane according to claim 2, special
Sign is: the additive one is one of tap water, distilled water, ultrapure water, deionized water or a variety of mixtures.
9. the method for biomass-based furfuryl alcohol derivative green high-efficient synthesis Coumarin methane according to claim 2, special
Sign is: the additive two includes: air, oxygen or a certain proportion of containing oxygen gas mixture.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110437182A (en) * | 2019-07-16 | 2019-11-12 | 南昌大学 | A method of BMFM is synthesized from 5-MFA green high-efficient |
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| CN110437182A (en) * | 2019-07-16 | 2019-11-12 | 南昌大学 | A method of BMFM is synthesized from 5-MFA green high-efficient |
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