CN108047175A - A kind of synthetic method of furanone - Google Patents
A kind of synthetic method of furanone Download PDFInfo
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- CN108047175A CN108047175A CN201711417267.0A CN201711417267A CN108047175A CN 108047175 A CN108047175 A CN 108047175A CN 201711417267 A CN201711417267 A CN 201711417267A CN 108047175 A CN108047175 A CN 108047175A
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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
- C07D307/56—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 invention discloses a kind of synthetic methods of furanone, belong to technical field of organic synthesis.This method includes：(1) 3,4 acetyl butyryls, Bromide, strong acid and oxidant are reacted in the in the mixed solvent of water and organic solvent A under the conditions of 10 60 DEG C, are stood after the completion of reaction, are taken organic phase；(2) cyclization catalyst and water are added in organic phase, gradually heating removes organic solvent, it then heats to reflux and carries out ring-closure reaction, cool down after the completion of reaction and alkali is added to adjust pH to 47, then it is concentrated under reduced pressure, organic solvent B is added in after the completion of concentration, Bromide is recovered by filtration for step (1), filtrate is concentrated to give furanone.The crude product purity that this method is drawn is more than 85%, and yield is more than 80%.This method applies mechanically sodium bromide, and it is excessively seldom that reaction system adds in bromine source, does not have bromine spilling in reaction process, solves the problems, such as that bromine pollutes environment, while it is short, easy to operate and be easy to industrialized production to have many advantages, such as to generate the cycle.
Description
Technical field
The present invention relates to technical field of organic synthesis, and in particular to a kind of synthetic method of furanone.
Background technology
Furanone（- 3 (2H)-furanone of 4- hydroxyl -2,5- dimethyl）It is the extremely wide natural safe fragrance of purposes, extensively should
It is nowadays increasing to furanone demand for industries such as food, beverage, tobacco, health products.Furanone is in the essence of China
There is irreplaceable status, therefore the furanone synthesis technology of developing low-cost, it appears particularly necessary in fragrance industry.
Some patents and document report on synthesis furanone both at home and abroad introduced below.
First, using carbohydrate as the synthetic route of raw material
Initial furanone is accidentally obtained by rhamnose, and Mia11adr degradations occur in alkaline conditions for fructose, D-Glucose
All contain furanone in the product of reaction.
(1) Decnop C, Van Dort J M, et al.EP 398417,1990. document reports by L- rhamnoses with
L-lysine is in NaH2PO4And Mai1lard reactions occur in Na0H media, the natural furanone that yield is 38% can be obtained；If
The natural furanone that can obtain that yield is 61% is reacted under similarity condition with L-fucose and L-lysine.
(2) Megulo H, Orui H, Fadaig K, Fugiat A.JP 0248594,1990. document reports are by grape
Sugar is raw material, it is made to be handled to obtain bis--O- isopropylidenes-a-D- of 1,2,5,6- with phosphate aqueous solution after mixing with acetone and zinc chloride
Glucofuranose, the latter handle 6h in 90 DEG C with mesyl chloride in DMF, obtain 6- deoxidations -6- chloro- 1,2:Bis- -0- of 3,5-
Isopropylidene-a-D-Glucose, the latter are handled with storng-acid cation exchange resin, obtain 6- deoxidation-D- glucopyranoses,
Finally with piperidines and acetic acid reflux 8h, furanone is obtained.
(3)Wong C H,et al.[J] J Org Chem,1983,48(20):3493. document reports, by D- fruits
Sugar -1,6- bisphosphates obtain 6- deoxidation fructose-1-phosphates under the action of two kinds of enzymes with a- hydroxy aldehydes (such as D- lactic aldehydes) effect
Ester is then hydrolyzed to 6- deoxidation fructose, then obtains furanone through piperidines acetic acid salt treatment.
(4) Whiitesides G M, Mazenod F P.EP 90150,1983. document reports are by fructose diphosphate
Furanone is made in the hydrogenation of the alkali or alkaline earth metal salt of ester and phosplate.
(5) 63307869,1988. document reports of Washino K, Imai S, Hoirkawa Y, Nishjmuar N.JP
In the presence of ion exchange resin, 6- deoxyhexamethyloses are handled with nitrogenous organic base, obtain furanone.
Above method does not have practical value to the preparation of furanone.This kind of universal route of method is partially long, some originals of raw material
Expect that price is high, product yield is low, and separate, purification it is more difficult.
2nd, using furan derivatives as the synthetic route of raw material
(1)Buchi G,Demole E.[J].J Org Chem,1973,38(1):123. document report is with 2,5- dimethyl
Furans electrolytic oxidation can generate 2,5- dimethoxy-2,5-dihydrofurans, then with KClO3,0s04Open loop is aoxidized, obtains 3,4- bis-
Hydroxyl -2,5- acetyl butyryls, then in saturation NaHCO3Middle cyclisation can obtain the furanone that yield is 51%.
(2) 466583,1992. document reports of Fellous R, George G.EP are so that 2,5- dimethyl furan ketone
In the presence of a base, furanone can be obtained with hydrogen peroxide oxidation.
(3) Eschinasi E H, Castelli E.US 4294767,1982. document reports with 2,5- dimethyl-
(2H) furanone of dihydro -3 and acetaldehyde dehydrating condensation obtain ketenes intermediate (yield 70%), then through ozone oxidation, reduction and hydrolysis
It can obtain the furanone of yield about 40%.
(4) Cohen A M, Lensnelink W, Van E C.EP 532120,1993. document reports using purity as
98.4% 5- methyl -3,4- dihydroxy -2- furyl ethyl formates and Na0H aqueous solutions place at room temperature 40 it is small when, it is dilute with water
After releasing, after with bromomethane and HCl processing, furanone is obtained.
It is this kind of that using furans or furan derivatives as the synthetic route of raw material, yield is not very high, and largely
It is limited be subject to raw material sources, is not suitable for industrialized production.
3rd, using unsaturated diol derivative as the synthetic route of raw material
(1)Ross K H,Dudeck C,Himmele W,Lebkuecher R,Sauer W.DE 2910131,1980. Ross
Et al. patent report:Make 3- hexene -2,5- glycol through H2O2-NaWO4/W03Catalysis oxidation, can be cyclized generation 2,5- dimethyl-
3,4 dihydroxy-tetrahydrofuran (yield 78%-85%), further oxidation can obtain furanone, total recovery 30%-35%.
(2) 474501,1969. document reports of Buchi G, Edouard D, et al.swiss, using 3- hexin -2,
5- glycol is through low temperature (- 2-- 30 DEG C) ozone oxidation and Ph3P is reduced, and the furanone that yield is 75% is can obtain in acidifying closed loop.
This kind of method raw material is not easy to obtain, and needs oneself to synthesize.And catalyst is expensive, and operation requirement is also higher, should
With being restricted, industrialized production is also not suitable for.
4th, using carboxylic acid derivates as the synthetic route of raw material
(1)De Rijke D,et al.[J].Rect Tvar Chim Pays-Bas,1973,92(6):731-738. document reports
Road makes ethyl acetoacetate be reacted with a- bromo propionyl chlorides in the presence of metallic sodium, first cyclisation and hydrolysis, then with H2O2In diluted alkaline
Oxidation generation epoxides, finally can be made the furanone that yield is 46% with sour water solution, and this method step is limited to raw material and is not easy
It obtains, it is difficult to applied to industrialized production.
(2)Briggs M A,Haines A H.[J].J Chem Soc,Perkin Trans I,1985(4),795.
Document report uses (2R, 3R)-tartaric acid (protecting vicinal diamines with acetone) that diamides intermediate can be made through esterification and aminolysis, then
With CH2Mgl reaction generation diketone, further hydrolytic cyclization can obtain the furanone that total recovery is 18.5%, and this method yield is too
It is low, up for further being promoted.
(3)Vanden Ouweland G,et al.[J].Rect Tvar Chim Pays-Bas,1974,93(12):
312-313. document reports using ethyl lactate (protecting hydroxyl with dihydropyran) in alkaline medium with condensation of acetone, then pass through
Bromo, acetylation and sour water solution can be made total recovery be 40% furanone, the method have raw material is inexpensive, is easy to get, synthetic route
It is short, it is each to walk the advantages that yield is higher.But metallic sodium is used in synthesizing, industrial production operation is inconvenient, needs further excellent
Change.
4th, using aldehyde ketone derivative as the synthetic route of raw material
(1)Buchi G,Demole E,et al.[J].J Org Chem,1973,38(l):123-125. document report, with third
Keto-aldehyde is raw material, is coupled in zinc powder and dilute acetic acid solution, through Na2HPO4The furans that yield total recovery is 28.6% is made in cyclisation
Ketone.Such synthetic route is short, and yield is medium, and reaction condition is mild, easy to operate.It is also referred in the literature using 3,4- acetyl butyryls
Bromination generates 2,5-, bis- bromo- 3,4- acetyl butyryls in ether-dioxane solvent, then can obtain yield through hydrolyzing closed loop as 46%
Furanone, both synthetic methods, operation it is easier, synthetic route is short, but is also limited be subject to raw material sources, solves original
The problem of material, the product purity that this method obtains is higher, can be used as industrialization promotion.
(2) 2845843,1979. document reports of Bruno B, Valerio C, Eletti B G.DE are with 1- butine -3- alcohol
It for raw material and grignard reagent reacting, then reacts with acetaldehyde and to increase by two carbon atoms and obtain required carbon skeleton, and generated at 2-
One new hydroxyl forms 2,5- dihydroxy acetylides, is then successively handled in polar solvent with ozone, triphenylphosphine
It arrives.The heating in blanket of nitrogen and in the presence of acidic catalyst of 2,5- dihydroxy -3,4- acetyl butyryls obtains furanone.It also can be in phenolic aldehyde
Stirring makes 2,5- dihydroxy -3,4- acetyl butyryl cyclizations into furanone, yield in aqueous solution in the presence of type cation exchange resin
For 32%.
(3) with 3,4- acetyl butyryls for raw material, 10-25 DEG C is added dropwise 101696198 B of Chinese patent CN reports without solvent
Bromine 5-6h, occurs substitution reaction, insulation reaction 3-6h, through 2,5-, bis- bromo- 3, the 4- that neutralizations, be evaporated in vacuo oneself two
Ketone, yield 70-90%.Then 2,5-, bis- bromo- 3,4- acetyl butyryls 60-90 DEG C of hydrolysis 6-12h, warp under alkali metal salt effect
It crosses and neutralizes, washs, extracting, concentrating, crystallizing, recrystallizing and to obtain product furanone, yield 50-60%, content is>98%.
The industrial process of present is：Using propionic aldehyde ketone as starting material, 3,4- acetyl butyryls, Ran Hou are synthesized first
Bromine is added under low temperature, generates the crude product of 2,5-, bis- bromo- 3,4- acetyl butyryls, 2, the 5- bis- bromo- 3 of high-purity is obtained by distillation,
4- acetyl butyryls, then the 60-90 DEG C of hydrolysis under alkali metal salt effect of 2,5-, bis- bromo- 3,4- acetyl butyryls is cyclic, by neutralizing, washing
Product furanone, yield 50-60% are washed, extract, concentrating, crystallizing, recrystallizing and to obtain, content is>98%.
Existing production method there are it is more the drawbacks of, used substantial amounts of bromine in reaction process, centre has largely
Bromination hydrogen generates, and hydrogen bromide is very big to the pollution of environment, due to cannot recovery, only inhaled by bromination hydrogen
It receives tower to absorb, eventually becomes hydrogen bromide solution.Second step cyclization generation sodium bromide also can not recovery, by-product can only be used as
Product are taken out, and the hydrogen bromide and the amount of sodium bromide that two steps generate are very big, are got up as byproduct for treatment extremely onerous.Bromine
Price it is very high, bromine it is incomplete using also resulting in increasing for production cost.
Based on case above, in order to solve the problem of environmental issue that hydrogen bromide brings and solve bromine not applying mechanically,
Production cost is reduced, in the case of using 3 4- acetyl butyryls as raw material, we employ a kind of new synthetic route and successfully synthesize
Furanone.The crude product purity drawn using this method is all higher than 85%, and yield is more than 80%.Eliminate intermediate many operation steps
Suddenly, synthesis cycle is greatly shortened, due to changing related raw material, bromine therein can be applied mechanically, and every batch of, which feeds intake, only to be needed to mend
Waste bromine is filled, since the inventory of bromine in reaction is equimolar amounts, the utilization rate of bromine is improved, and has added
Solvent only has minimal amount of hydrogen bromide gas overflowing in reaction, without setting special hydrogen bromide recovery tower, removed bromine less
Change the recovery process of hydrogen, alleviate environmental protection pressure.Cyclization process is hydrolyzed, adds a kind of specific cyclization catalyst so that most
Yield afterwards improves 10% or so.
The content of the invention
An embodiment of the present invention provides a kind of synthetic methods of furanone, and compared with existing process method, this method is not required to
It to need as prior art using complicated synthetic method, separation method and the environmental protection of the bromine subsequently considered is needed to ask
The recycling problem of topic and bromine.Existing production technology is using bromine as raw material, in feeding intake for first step oxidation, wherein have one
A bromine atoms can utilize and produce bis- bromo- 3,4- acetyl butyryls of 2,5-.A remaining bromine atoms then become hydrogen bromide co-product,
So the utilization rate highest of bromine atoms also only has 50%, the bromine atoms of this patent then can all be transformed into 2,5-, bis- bromo- 3,4- oneself
Diketone, utilization rate can theoretically reach 100%, the first step without or substantially seldom hydrogen bromide generate, without specially setting bromine
Change the recovery system of hydrogen.The crude product purity obtained using this method is more than 85%, and yield is more than 80%.This method has production efficiency
It is high, low energy consumption, solvent consumption is few, safety and environmental protection, equipment cost are low, easy to operate, the advantages that being easy to industrialized production.The skill
Art scheme is as follows.
An embodiment of the present invention provides a kind of synthetic method of furanone, this method includes：
(1) 3,4- acetyl butyryls, Bromide（Sodium bromide, potassium bromide or bromination reason etc.）, strong acid and oxidant be in water and organic solvent A
In the mixed solvent reacted under the conditions of 10-60 DEG C, stood after the completion of reaction, reaction liquid layer, react salt and the centre of generation
Product（Bis- bromo- 3,4- acetyl butyryls of mainly 2,5- also have other intermediate products, but can finally be converted to target product）
Water phase and organic phase are respectively enterd, takes organic phase.Wherein, the molar ratio of Bromide, strong acid, oxidant and 3,4- acetyl butyryl is
1.5-2.5:1.5-2.5:1.5-2.5:1。
In this step, substantial amounts of hydrogen bromide can be generated, but in the mixed solvent, water is used not only for dissolving Bromide,
It is additionally operable to the salt of dissolving reaction generation；Organic solvent avoids bromine from overflowing for preferably dissolving bromine.In addition, in the process
In, overflow no hydrogen bromide with specific solvent by specifically matching.
(2) cyclization catalyst and water are added in organic phase, gradually heating removes organic solvent, then heats to and flows back into
Row ring-closure reaction, cooling and plus the corresponding alkali of Bromide after the completion of reaction（Sodium hydroxide, potassium hydroxide or lithium hydroxide etc.）It adjusts
Whole pH to 4-7, is then concentrated under reduced pressure, and organic solvent B is added in after the completion of concentration, and Bromide is recovered by filtration and is realized for step (1)
Recycling bromine is applied mechanically, and filtrate is concentrated to give furanone.In this process, substantial amounts of water can be added in, the bromine for generating ring-closure reaction
Change hydrogen concentration is very low, and the condenser only carried by reaction kettle can avoid hydrogen bromide from discharging；In addition, pass through specific cyclization
The addition of catalyst, can not only accelerate reaction speed reduces the risk that hydrogen bromide overflows, moreover it is possible to improve 10% or so yield.
Wherein, in step (1), organic solvent A is selected from chloroform, dichloromethane, ethyl acetate or butyl acetate etc.,
Preferably chloroform.
Further, in step (1), the mass ratio of organic solvent A, water and 3,4- acetyl butyryl is 1-2:1-2:1.
Wherein, in step (1), oxidant be selected from hydrogen peroxide, sodium hypochlorite, postassium hypochlorite, sodium hypobromite, sodium bromate or
Potassium bromate etc..Preferably, oxidant can avoid the introducing of impurity for hydrogen peroxide；Specifically, the concentration of hydrogen peroxide is 20-35wt%.
Wherein, in step (1), strong acid can be specifically the concentrated sulfuric acid, the concentration of the concentrated sulfuric acid is specific for providing hydrogen ion
Can be 70-98wt%.
Wherein, in step (1), when reaction time 6-24 is small, gas-chromatography tracking reaction process may be employed.
Wherein, in step (2), cyclization catalyst is vitamin E polyethanediol succinate（Single, double ester or both is appointed
The mixture of what ratio）Or methoxyl group vitamin E polyethanediol succinate；Wherein, the molecular weight of polyethylene glycol is 400-
Between 2000.Preferably, cyclization catalyst is methoxyl group vitamin E polyethanediol succinate.It is highly preferred that cyclization is catalyzed
Agent is methoxyl group vitamin E polyethylene glycol-1000 succinate.
Further, in step (2), the mass ratio of cyclization catalyst, water and 3,4- acetyl butyryl is 0.01-0.05:24-
36:1, water consumption is very big, can not only be overflowed to avoid hydrogen bromide, can also avoid intermolecular condensation, improves reaction yield.
Wherein, in step (1), Bromide for sodium bromide, potassium bromide or bromination reason etc., correspondingly, in step (2),
Alkali is sodium hydroxide, potassium hydroxide or lithium hydroxide etc..Preferably, in step (1), Bromide is sodium bromide；Correspondingly, exist
In step (2), alkali is sodium hydroxide, and concentration can be 1-10wt%.
Wherein, in step (2), the reaction time of ring-closure reaction is 6-24h.
Wherein, in step (2), the condition being concentrated under reduced pressure is：Temperature is less than 70 DEG C, and pressure is less than -0.098Mpa.
Wherein, in step (2), organic solvent B is selected from chloroform, dichloromethane, methyl acetate, ethyl acetate, second
One or more in propyl propionate, isopropyl acetate and butyl acetate etc.；Preferably ethyl acetate.
Preferably, synthetic method provided by the invention includes：
(1) 3,4- acetyl butyryls, sodium bromide and 70-98wt% sulfuric acid, Ran Houhuan are added in the in the mixed solvent of water and organic solvent A
It is slow to add in or be added dropwise 20-35wt% hydrogen peroxide, when reaction 12-24 is small under the conditions of 10-60 DEG C, stands, take organic after the completion of reaction
Phase.
Wherein, organic solvent A is selected from chloroform, dichloromethane, ethyl acetate or butyl acetate etc., organic solvent A, water
Mass ratio with 3,4- acetyl butyryls is 1-2:1-2:1, sodium bromide, sulfuric acid（70-98wt%）, hydrogen peroxide（20-35wt%）With 3,4-
The mass ratio of acetyl butyryl is 1.8-2.0:0.8-1.0:1.9-2.5:1.
(2) cyclization catalyst and water are added in organic phase, is gradually heated up, organic solvent is removed, then heats to reflux
8-16h is reacted, room temperature is down to after the completion of reaction, sodium hydroxide solution adjustment pH to 4-7 is added dropwise（Preferably 5-6）, then small
It is concentrated under reduced pressure under the conditions of 70 DEG C, organic solvent B is added in after the completion of concentration, sodium bromide is recovered by filtration for step (1), filtrate is dense
Contracting obtains furanone.
Wherein, cyclization catalyst is vitamin E polyethanediol succinate or methoxyl group vitamin E polyethylene glycol amber
Acid esters, the molecular weight of polyethylene glycol is between 400-2000；The mass ratio of cyclization catalyst, water and 3,4- acetyl butyryls is 0.01-
0.05:24-36:1。
It is highly preferred that method provided by the invention includes：By water, chloroform, 3,4- acetyl butyryls, sodium bromide, the concentrated sulfuric acid
It putting into reaction kettle, then 30wt% hydrogen peroxide is slowly added dropwise, controlling reaction temperature is 20 DEG C, and reaction time 16h takes organic phase,
Water and cyclization catalyst methoxyl group vitamin E polyethanediol succinate are added in, is progressively heated up, early period collects chloroform.
Chloroform collection finishes, and begins to warm to 100 DEG C of reflux, reaction time 12h.Reaction finishes, and cools to room temperature, is added dropwise
Between the pH of solution is adjusted to 5-6 by the sodium hydroxide solution of 5wt%, then t<70℃,p<It is under the conditions of -0.098Mpa, system is dense
Shorten into it is dry, add in ethyl acetate stirring, room temperature filtering, filter residue for recycling sodium bromide solid.The sodium bromide of recycling can be used for
The raw material of front feeds intake, and then directly concentration is dry for obtained filtrate, obtains the crude product of furanone.Wherein, sodium bromide, sulfuric acid, dioxygen
Water, water（Reaction is used）, organic solvent A, cyclization catalyst, water（Cyclization is used）Mass ratio with 3,4- acetyl butyryls is 1.8-2.0:
0.8-1.0:1.9-2.5:1-2:1-2:0.01-0.05:24-36:1。
The present invention has the following advantages：
1. the synthetic method avoids the generation of a large amount of bromination hydrogen by changing starting material.
2. this method changes mode of operation, synthesis cycle is greatly shortened, simplifies operating procedure, improves efficiency,
Energy consumption is reduced.
3. there is no hydrogen bromide gas overflowing in reaction process, solves the problem of environmental pollution that hydrogen bromide is brought.
4. solving the problems, such as applying mechanically for bromine, the utilization rate of bromine is greatly improved, it is not necessary to carry out the byproduct of bromine
Turnover is taken out, the fund that bromine greatly reduces overstocks cost.
5. this method adds a kind of new cyclization catalyst so that cyclization efficiency greatly promotes, in the quality of product
In the case of aspect is undiminished, product yield is obviously improved.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, embodiment of the present invention is made below further
It is described in detail on ground.
Embodiment 1（Comparison synthesis）
(1) in 250ml three-necked flasks, input 11.4g water, 11.4g chloroforms, 11.4g 3,4- acetyl butyryls, 20.6g bromines
Change sodium, 9.8g sulfuric acid input wherein, the hydrogen peroxide that 22.6g 30% is slowly added dropwise carries out redox reaction, controlling reaction temperature
For 20 DEG C, reaction time 12h.
(2) after the completion of reacting, organic layer is collected separately in reaction solution stratification, is transferred to the three-necked flask of a 500ml
In, add in 280g water（It is not added with cyclization catalyst）, progressively heat up, collect chloroform early period, chloroform collection is finished, started
It is warming up to 100 DEG C of reflux, reaction time 8h.
(3) reaction terminates, and reaction solution cooled to room temperature, is added dropwise between the pH of solution is adjusted to 5-6 by lye, then t<
70℃,p<It is under the conditions of -0.098Mpa, system is dense dry.
(4) solid adds in the stirring of 50g ethyl acetate, and then room temperature filters, and recycles filter residue sodium bromide solid 13.8g, recycling
Yield is 67%（On the basis of the sodium bromide that feeds intake, the recycling of sodium bromide is calculated）.The sodium bromide of recycling can be used for the raw material of front
It feeds intake.Filtrate, which directly concentrates, does, and obtains the crude product of furanone, weight 9.35g, purity 86%, yield 62.8%（To feed intake
On the basis of acetyl butyryl, yield is molar yield）.
Embodiment 2（Comparison synthesis）
(1) in 250ml three-necked flasks, input 11.4g water, 11.4g chloroforms, 11.4g 3,4- acetyl butyryls, 20.6g bromines
Change sodium, 9.8g sulfuric acid input wherein, the hydrogen peroxide that 22.6g 30% is slowly added dropwise carries out redox reaction, controlling reaction temperature
For 20 DEG C, reaction time 12h.
(2) after the completion of reacting, organic layer is collected separately in reaction solution stratification, is transferred to the three-necked flask of a 500ml
In, add in 420g water（It is not added with cyclization catalyst）, progressively heat up, collect chloroform early period, chloroform collection is finished, started
It is warming up to 100 DEG C of reflux, reaction time 8h.
(3) reaction terminates, and reaction solution cooled to room temperature, is added dropwise between the pH of solution is adjusted to 5-6 by lye, then t<
70℃,p<It is under the conditions of -0.098Mpa, system is dense dry.
(4) solid adds in the stirring of 50g ethyl acetate, and then room temperature filters, and recycles filter residue sodium bromide solid 14.5g, recycling
Yield is 70%.The raw material that the sodium bromide of recycling can be used for front feeds intake.Filtrate, which directly concentrates, does, and obtains the crude product of furanone,
Weight is 10.46g, purity 88%, yield 71.9%.
Embodiment 3（Using synthesis）
(1) in 250ml three-necked flasks, input 11.4g water, 11.4g chloroforms, 11.4g 3,4- acetyl butyryls, 20.6g bromines
Change sodium, 9.8g sulfuric acid input wherein, the hydrogen peroxide that 22.6g 30% is slowly added dropwise carries out redox reaction, controlling reaction temperature
For 20 DEG C, reaction time 12h.
(2) after the completion of reacting, organic layer is collected separately in reaction solution stratification, is transferred to the three-necked flask of a 500ml
In, add in 420g water, 0.2g cyclization catalysts（Vitamin E polyethylene glycol-1000 succinate）, progressively heat up, early period collects
Chloroform, chloroform collection finish, and begin to warm to 100 DEG C of reflux, reaction time 8h.
(3) reaction terminates, and reaction solution cooled to room temperature, is added dropwise between the pH of solution is adjusted to 5-6 by lye, then t<
70℃,p<It is under the conditions of -0.098Mpa, system is dense dry.
(4) solid adds in the stirring of 50g ethyl acetate, and then room temperature filters, and recycles filter residue sodium bromide solid 15.4g, recycling
Yield is 74.6%.The raw material that the sodium bromide of recycling can be used for front feeds intake.Filtrate, which directly concentrates, does, and obtains the thick of furanone
Product, weight 11.95g, purity 87%, yield 81.2%.
Embodiment 4
(1) in 250ml three-necked flasks, input 11.4g water, 11.4g chloroforms, 11.4g 3,4- acetyl butyryls, 20.6g bromines
Change sodium, 9.8g sulfuric acid input wherein, the hydrogen peroxide that 22.6g 30% is slowly added dropwise carries out redox reaction, controlling reaction temperature
For 20 DEG C, reaction time 12h.
(2) after the completion of reacting, organic layer is collected separately in reaction solution stratification, is transferred to the three-necked flask of a 500ml
In, add in 420g water, 0.2g cyclization catalysts（Methoxyl group vitamin E polyethylene glycol-1000 succinate）, progressively heat up, it is preceding
Phase collects chloroform, and chloroform collection finishes, and begins to warm to 100 DEG C of reflux, reaction time 8h.
(3) reaction terminates, and reaction solution cooled to room temperature, is added dropwise between the pH of solution is adjusted to 5-6 by lye, then t<
70℃,p<It is under the conditions of -0.098Mpa, system is dense dry.
(4) solid adds in the stirring of 50g ethyl acetate, and then room temperature filters, and recycles filter residue sodium bromide solid 16.75g, recycling
Yield is 81.3%.The raw material that the sodium bromide of recycling can be used for front feeds intake.Filtrate, which directly concentrates, does, and obtains the thick of furanone
Product, weight 12g, purity 88%, yield 82.8%.
Embodiment 5
(1) in 1000ml three-necked flasks, input 114g water, 114g chloroforms, 114g 3,4- acetyl butyryls, 206g brominations
Wherein, the hydrogen peroxide that 226g 30% is slowly added dropwise carries out redox reaction, controlling reaction temperature 20 for sodium, 98g sulfuric acid input
DEG C, reaction time 12h.
(2) after the completion of reacting, organic layer is collected separately in reaction solution stratification, is transferred in the three-necked flask of a 5L,
Add in 4.2Kg water, 2.0g cyclization catalysts（Methoxyl group vitamin E polyethylene glycol-1000 succinate）, progressively heat up, early period
Chloroform is collected, chloroform collection finishes, and begins to warm to 100 DEG C of reflux, reaction time 8h.
(3) reaction terminates, and reaction solution cooled to room temperature, is added dropwise between the pH of solution is adjusted to 5-6 by lye, then t<
70℃,p<It is under the conditions of -0.098Mpa, system is dense dry.
(4) solid adds in the stirring of 500g ethyl acetate, and then room temperature filters, and recycles filter residue sodium bromide solid 178.6g, returns
It is 86.7% to receive yield.The raw material that the sodium bromide of recycling can be used for front feeds intake.Filtrate, which directly concentrates, does, and obtains furanone
Crude product, weight 111.4g, purity 87%, yield 83.2%.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modifications, equivalent replacements and improvements are made should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of synthetic method of furanone, which is characterized in that the described method includes：
(1) 3,4- acetyl butyryls, Bromide, strong acid and oxidant in the in the mixed solvent of water and organic solvent A in 10-60 DEG C of condition
Lower reaction stands after the completion of reaction, takes organic phase, and the Bromide, strong acid, the molar ratio of oxidant and 3,4- acetyl butyryl are
1.5-2.5:1.5-2.5:1.5-2.5:1；
(2) cyclization catalyst and water are added in organic phase, gradually heating removes organic solvent, then heats to reflux and carries out ring
Reaction is closed, cool down after the completion of reaction and adds the corresponding alkali adjustment pH to 4-7 of Bromide, is then concentrated, being added in after the completion of concentration has
Bromide is recovered by filtration for step (1) in solvent B, and filtrate is concentrated to give furanone.
2. the synthetic method of furanone according to claim 1, which is characterized in that in step (1), the organic solvent
A is selected from chloroform, dichloromethane, ethyl acetate or butyl acetate.
3. the synthetic method of furanone according to claim 1, which is characterized in that in step (1), the organic solvent
A, the mass ratio of water and 3,4- acetyl butyryls is 1-2:1-2:1.
4. the synthetic method of furanone according to claim 1, which is characterized in that in step (1), the oxidant choosing
From hydrogen peroxide, sodium hypochlorite, postassium hypochlorite, sodium hypobromite, sodium bromate or potassium bromate.
5. the synthetic method of furanone according to claim 1, which is characterized in that in step (1), the oxidant is
Hydrogen peroxide.
6. the synthetic method of furanone according to claim 1, which is characterized in that in step (2), the cyclization is urged
Agent is vitamin E polyethanediol succinate or methoxyl group vitamin E polyethanediol succinate.
7. the synthetic method of the furanone according to claim 1 or 6, which is characterized in that in step (2), the cyclization
The mass ratio of catalyst, water and 3,4- acetyl butyryls is 0.01-0.05:24-36:1.
8. the synthetic method of furanone according to claim 1, which is characterized in that in step (1), the Bromide is
Sodium bromide, potassium bromide or lithium bromide, correspondingly, in step (2), the alkali is sodium hydroxide, potassium hydroxide or lithium hydroxide.
9. the synthetic method of furanone according to claim 1, which is characterized in that in step (2), the organic solvent
B in chloroform, dichloromethane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate and butyl acetate one
Kind is a variety of.
10. the synthetic method of furanone according to claim 1, which is characterized in that the described method includes：
(1) 3,4- acetyl butyryls, sodium bromide and 70-98wt% sulfuric acid, Ran Houhuan are added in the in the mixed solvent of water and organic solvent A
It is slow to add in or be added dropwise 20-35wt% hydrogen peroxide, when reaction 12-24 is small under the conditions of 10-60 DEG C, stands, take organic after the completion of reaction
Phase；
Wherein, the organic solvent A be selected from chloroform, dichloromethane, ethyl acetate or butyl acetate, the organic solvent A,
The mass ratio of water and 3,4- acetyl butyryls is 1-2:1-2:1, the sodium bromide, sulfuric acid, the mass ratio of hydrogen peroxide and 3,4- acetyl butyryl
For 1.8-2.0:0.8-1.0:1.9-2.5:1；
(2) cyclization catalyst and water are added in organic phase, is gradually heated up, organic solvent is removed, then heats to back flow reaction
8-16h is down to room temperature after the completion of reaction, sodium hydroxide solution adjustment pH to 4-7 is added dropwise, is then depressurized under the conditions of less than 70 DEG C
Concentration adds in organic solvent B after the completion of concentration, sodium bromide is recovered by filtration for step (1), filtrate is concentrated to give furanone；
Wherein, the cyclization catalyst is vitamin E polyethanediol succinate or methoxyl group vitamin E polyethylene glycol amber
Acid esters, the mass ratio of the cyclization catalyst, water and 3,4- acetyl butyryl is 0.01-0.05:24-36:1.
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| CN110669029A (en) * | 2019-10-25 | 2020-01-10 | 安徽金轩科技有限公司 | Environment-friendly process equipment for synthesizing furanone |
| CN111517507A (en) * | 2019-02-01 | 2020-08-11 | 兆联实业股份有限公司 | Water treatment system |
| CN112047911A (en) * | 2020-09-18 | 2020-12-08 | 厦门欧米克生物科技有限公司 | Catalytic synthesis method of furanone |
| CN112851549A (en) * | 2021-03-11 | 2021-05-28 | 安徽云帆药业有限公司 | Experiment method for sodium bromide application |
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| CN101696198B (en) * | 2009-10-28 | 2011-12-21 | 大连来克精化有限公司 | Preparation method of 2,5-dimethyl-4-oxhydryl-3(2H) furanone |
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|---|---|---|---|---|
| CN111517507A (en) * | 2019-02-01 | 2020-08-11 | 兆联实业股份有限公司 | Water treatment system |
| CN110669029A (en) * | 2019-10-25 | 2020-01-10 | 安徽金轩科技有限公司 | Environment-friendly process equipment for synthesizing furanone |
| CN112047911A (en) * | 2020-09-18 | 2020-12-08 | 厦门欧米克生物科技有限公司 | Catalytic synthesis method of furanone |
| CN112851549A (en) * | 2021-03-11 | 2021-05-28 | 安徽云帆药业有限公司 | Experiment method for sodium bromide application |
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