CN110372646A - A kind of preparation method of furanone - Google Patents
A kind of preparation method of furanone Download PDFInfo
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- CN110372646A CN110372646A CN201910795094.9A CN201910795094A CN110372646A CN 110372646 A CN110372646 A CN 110372646A CN 201910795094 A CN201910795094 A CN 201910795094A CN 110372646 A CN110372646 A CN 110372646A
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- 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
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Abstract
The invention discloses a kind of preparation method of furanone, the preparation including pyroracemic aldehyde solution, the preparation of 3,4- dihydroxy-2,5-hexanedione solution, the purification of 3,4- dihydroxy-2,5-hexanediones, the preparation of furanone semi-finished product, the preparation of finished product furanone.The invention has the advantages that 1. can be improved the yield of intermediate product 3,4- dihydroxy -2,5- acetyl butyryl and the gross production rate of furanone by composite catalyst zinc powder, iron powder and manganese powder；2. by the way that anhydrous sodium sulphate and sodium chloride composite granule is added, hence it is evident that improve intermediate product 3, the purity of 4- dihydroxy-2,5-hexanedione；3. the purity of furanone can be significantly improved by combination extractant ethyl alcohol and ethyl acetate.
Description
Technical field
The invention belongs to chemical production technical fields, are related to a kind of preparation method of furanone.
Background technique
The natural product of furanone are present in strawberry, oat, cheese, Boiled beef, beer, cocoa, coffee, tealeaves, mango, litchi
In branch, malt, dayberry, grape, heating beef, pineapple etc., nineteen sixty-five isolates furan in the ether extraction liquid of pineapple juice for the first time
It mutters ketone, and its molecular structural formula has been determined.With the furanone that it is synthesized, simple process and low cost, aroma of pure.It is practical at present
In production process it is more be with pyroracemic aldehyde and zinc powder reaction reductive coupling obtain 3,4- dihydroxy -2,5- acetyl butyryl, then
Furanone is made through being cyclized.
The generally existing reaction controlling of pyroracemic aldehyde method technique is difficult, supervene hydrogen thus security risk it is big, yield is not
It is too high, the problems such as three wastes (mainly brine waste) are seriously polluted.For example essence is opened positioned on document (" fine chemistry industry " 2001 the 18th
Roll up the 1st phase page 31~33) in using pyroracemic aldehyde as raw material, make coupling agent with zinc powder, suitable lithium chloride and the iodate tetrabutyl be added
Ammonium, the acetum for being added dropwise 15% react to obtain 2,5- dihydroxy -3,4- acetyl butyryl, then carry out cyclization, obtain after extracting
Obtain furanone；Room liter etc. is in document (" colleges and universities' chemical engineering journal " the 2nd phase page 233~237 of volume 19 in 2005) in acetone
A certain amount of zinc powder is added portionwise in aldehyde and acetic acid aqueous solution and reacts to obtain 3,4- dihydroxy -2,5- acetyl butyryl, then carries out ring
Change reaction, furanone is obtained after extracting；Zhang Ping is at document (volume 14 the 4th of " Lianyungang Technical College's journal " 2001
Phase page 13~14) in report pyroracemic aldehyde aqueous solution in zinc powder is added, the rear acetum that is added dropwise reacts to obtain 2,5- dihydroxy -3
, 4- acetyl butyryl then carries out cyclization, furanone obtained after extracting.Because of pre-add in reaction process in existing report
It is big that acid will cause reaction system acidity, cause zinc powder with it is sour it is preferential occur displacement react thus consumption increase, can also generate largely
Hydrogen brings serious danger, and system acidity is excessive to cause unstable products that side reaction influence yield occurs.Patent document
It uses acetate as reaction acidity controlling agent in CN109879742A, is continuously provided needed for reaction and sulfuric acid continuously is added dropwise
Low-concentration hydrogen ion, reactant pyroracemic aldehyde passes through reductive coupling reaction under the effect of the catalyst, obtains target product 3,
The reaction solution of 4- dihydroxy -2,5- acetyl butyryl, is filtered, and is extracted, and concentration, crystallization can be prepared by pure dihydroxy -2 3,4-,
5- acetyl butyryl.Although CN109879742A reduces side reaction to a certain extent, supplies consumption is reduced, production is comparatively safe, but still
So there are 3,4- dihydroxy -2,5- acetyl butyryl yield is lower, the lower problem of purity equally exists 3,4- in other documents
Dihydroxy -2,5- acetyl butyryl intermediate product yield is lower, purity is lower, and obtained final products furanone gross production rate and
The lower problem of purity.
Summary of the invention
The purpose of the present invention is to solve existing pyroracemic aldehyde methods to prepare in furanone, intermediate product 3,4- dihydroxy-
2,5- acetyl butyryl intermediate products and the problem that furanone gross production rate is lower, purity is lower, now provide a kind of yield and purity is equal
The preparation method of higher furanone.
In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical scheme:
A kind of preparation method of furanone, specific preparation process is as follows:
(1) preparation of pyroracemic aldehyde solution: silver catalyst is added in oxidator, then 1,2-PD is added to oxidator
In, it is passed through air, is heated to 360-380 DEG C, catalytic oxidation is carried out and generates pyroracemic aldehyde, it is dense then to absorb acquisition quality through water
Degree is pyroracemic aldehyde solution, spare；
(2) preparation of 3,4- dihydroxy -2,5- acetyl butyryl solution: it be furnished with thermometer, constant pressure funnel, mechanical stirring device
In the four-hole boiling flask of gas-guide tube, 45-55mL pure water, 10-20g sodium acetate and 1-2g tetrabutylammonium iodide, stirring and dissolving is added
Zinc powder, iron powder and manganese powder are added afterwards, 35-45mL pyroracemic aldehyde aqueous solution and 10-20mL dilute sulfuric acid is added dropwise, process control temp is added dropwise
It is 15-25 DEG C, adds zinc powder, iron powder and manganese powder, then 35-45mL pyroracemic aldehyde aqueous solution and 10-20mL dilute sulfuric acid is added dropwise simultaneously,
It is warming up to 30-45 DEG C of heat preservation 1-4 hours after dripping, obtains 3,4- dihydroxy-2,5-hexanedione solution, 3,4- dihydroxy -2,
The yield of 5- acetyl butyryl is 73% or more；
(3) purification of 3,4- dihydroxy -2,5- acetyl butyryl: in 3,4- dihydroxy -2,5- acetyl butyryl solution be added anhydrous sodium sulphate and
Sodium chloride is centrifuged, recycling, the liquid phase isolated in zinc powder, iron powder and the manganese powder return step (2) isolated
Acetate extractant is added to be extracted, extraction carries out acquisition extraction solution in second level extraction tower, then carries out oil and mutually steams
Hair concentration, recycles ethyl acetate and distilled water, obtains extraction concentrate；After freezing and crystallizing, centrifuge separation obtains 3,4- bis-
Hydroxyl -2,5- acetyl butyryl mother liquor and the 3,4- dihydroxy -2,5- acetyl butyryl by purifying；
(4) preparation of furanone semi-finished product: butyl acetate, water, phosphorus is added in the 3,4- dihydroxy -2,5- acetyl butyryl after purification of learning from else's experience
Acid dihydride sodium, sodium hydroxide pass through 10-14 hours cyclizations at 70-90 DEG C, after fully reacting, after standing a period of time,
Separate fuel-displaced phase and water phase；The water phase returns to cyclization by concentration and recovery sodium dihydrogen phosphate, and waste water is discharged；The oil
Mutually pass through concentration and recovery butyl acetate, and obtains liquid phase furanone semi-finished product；
(5) liquid phase furanone semi-finished product the preparation of finished product furanone: are obtained into crude product furans by freezing and crystallizing, centrifuge separation
Crude product furanone is dissolved into ethyl alcohol and ethyl acetate extracts by ketone, and the volume ratio of ethyl alcohol and ethyl acetate is 1:(1.1-
2), after filtering out impurity, freezing and crystallizing, centrifuge separation acquisition furanone finished product is carried out, wet furanone finished product is dried
It is dry, obtain finished product furanone.
Further, the mass concentration of pyroracemic aldehyde solution is 20%-30% in the step (1) and step (2).
Further, the mass concentration of dilute sulfuric acid described in the step (2) is 30%-50%.
Further, the mass ratio of zinc powder, iron powder and manganese powder described in the step (2) is (3-5): (2-3): (1:3).
Further, acetate described in the step (2) is sodium acetate, potassium acetate, zinc acetate, lithium acetate, calcium acetate
In it is one or more.
Further, dropwise addition process control temp described in the step (2) is 20 DEG C
Further, it is warming up to 35 DEG C after dripping described in the step (2) and keeps the temperature 2 hours.
Further, the mass ratio of anhydrous sodium sulphate described in the step (3) and sodium chloride is (2-4): (1-3).
Further, cyclization temperature described in the step (4) is 80 DEG C.
Further, the cyclization time described in the step (4) is 12h.
Beneficial effects of the present invention:
In the preparation of (1) 3,4- dihydroxy-2,5-hexanedione, in catalyst zinc powder and iron powder be added manganese powder when, by zinc powder,
The synergistic effect of iron powder and manganese powder, can significantly improve the yield of 3,4- dihydroxy-2,5-hexanedione, and zinc powder, iron powder and
The mass ratio of manganese powder is (3-5): (2-3): when (1:3), the yield of 3,4- dihydroxy-2,5-hexanediones can reach 87% or more,
Intermediate product 3, the yield of 4- dihydroxy-2,5-hexanedione are greatly improved, and then the gross production rate of product is also improved.
In the purification step of (2) 3,4- dihydroxy-2,5-hexanedione, by the way that anhydrous sodium sulphate and sodium chloride composite granule is added,
It can be improved extraction efficiency, hence it is evident that improve intermediate product 3, the purity of 4- dihydroxy-2,5-hexanedione, in anhydrous sodium sulphate and sodium chloride
Mass ratio be (2-4): when (1-3), the purity of 3,4- dihydroxy-2,5-hexanediones is 99.91% or more.
(3) in the preparation of finished product furanone, by combination extractant ethyl alcohol and ethyl acetate, furanone can be significantly improved
Purity, the volume ratio of ethyl alcohol and ethyl acetate be 1:(1.1-2) when, the purity of furanone is 99.93% or more.
Specific embodiment
Embodiment 1:
(1) preparation of pyroracemic aldehyde solution: 4g silver catalyst is added in oxidator, then 1,2-PD is added to oxidator
In, it is passed through air, is heated to 370 DEG C, catalytic oxidation is carried out and generates pyroracemic aldehyde, then absorbing acquisition mass concentration through water is
25% pyroracemic aldehyde solution, it is spare.
(2) preparation of 3,4- dihydroxy -2,5- acetyl butyryl solution: it be furnished with thermometer, constant pressure funnel, mechanical stirring
In the four-hole boiling flask of device and gas-guide tube, 50mL pure water, 15g sodium acetate and 1g tetrabutylammonium iodide is added, adds after stirring and dissolving
Enter 3g zinc powder, 3g iron powder and 2g manganese powder, be added dropwise 40mL mass concentration 25% pyroracemic aldehyde aqueous solution and 15mL concentration 50% it is dilute
Sulfuric acid is added dropwise 20 DEG C of process control temp, adds 3g zinc powder, 3g iron powder and 2g manganese powder, then 40mL concentration 25% is added dropwise simultaneously
Pyroracemic aldehyde aqueous solution and 15mL concentration 50% dilute sulfuric acid, be warming up to after dripping 35 DEG C keep the temperature 2 hours, obtain 3,4- dihydroxy
Base -2,5- acetyl butyryl solution, the yield of 3,4- dihydroxy-2,5-hexanediones are 88.6%.
(3) 3g member the purification of 3,4- dihydroxy -2,5- acetyl butyryl: is added in 3,4- dihydroxy -2,5- acetyl butyryl solution
Bright powder and 2g sodium chloride, are centrifuged, recycling in zinc powder, iron powder and the manganese powder return step (2) isolated, separation
Liquid phase out is added acetate extractant and is extracted, and extraction carries out acquisition extraction solution in second level extraction tower, with laggard
Row oil is mutually concentrated by evaporation, and recycles ethyl acetate and distilled water, obtains extraction concentrate；After freezing and crystallizing, centrifuge separation is obtained
Obtain 3,4- dihydroxy-2,5-hexanedione mother liquor and 3, the 4- dihydroxy-2,5-hexanedione by purification, 3,4- dihydroxy -2,5-
The purity of acetyl butyryl is 99.93%.
(4) preparation of furanone semi-finished product: 50mL second is added in the 3,4- dihydroxy -2,5- acetyl butyryl 10g after purification of learning from else's experience
Acid butyl ester, 50mL water, 2.7g sodium dihydrogen phosphate, 2g sodium hydroxide pass through 12 hours cyclizations, fully reacting at 80 DEG C
Afterwards, after standing a period of time, fuel-displaced phase and water phase are separated；The water phase returns to cyclisation instead by concentration and recovery sodium dihydrogen phosphate
It answers, and waste water is discharged；The oil mutually passes through concentration and recovery butyl acetate, and obtains liquid phase furanone semi-finished product.
(5) liquid phase furanone semi-finished product the preparation of finished product furanone: are obtained into crude product furan by freezing and crystallizing, centrifuge separation
It mutters ketone, crude product furanone is dissolved into 25mL ethyl alcohol and 50mL ethyl acetate extracts, after filtering out impurity, carry out cold
Freeze brilliant, centrifuge separation and obtain furanone finished product, wet furanone finished product is dried, finished product furanone is obtained, obtains furans
The purity of ketone is 99.94%, gross production rate 79.7%.
Embodiment 2:
(1) preparation of pyroracemic aldehyde solution: 3g silver catalyst is added in oxidator, then 1,2-PD is added to oxidator
In, it is passed through air, is heated to 360 DEG C, catalytic oxidation is carried out and generates pyroracemic aldehyde, then absorbing acquisition mass concentration through water is
25% pyroracemic aldehyde solution, it is spare.
(2) preparation of 3,4- dihydroxy -2,5- acetyl butyryl solution: it be furnished with thermometer, constant pressure funnel, mechanical stirring
In the four-hole boiling flask of device and gas-guide tube, 50mL pure water, 15g potassium acetate and 1g tetrabutylammonium iodide is added, adds after stirring and dissolving
Enter 4g zinc powder, 2g iron powder and 3g manganese powder, be added dropwise 40mL mass concentration 25% pyroracemic aldehyde aqueous solution and 15mL concentration 50% it is dilute
Sulfuric acid is added dropwise 20 DEG C of process control temp, adds 4g zinc powder, 2g iron powder and 3g manganese powder, then 40mL concentration 25% is added dropwise simultaneously
Pyroracemic aldehyde aqueous solution and 15mL concentration 50% dilute sulfuric acid, be warming up to after dripping 35 DEG C keep the temperature 2 hours, obtain 3,4- dihydroxy
Base -2,5- acetyl butyryl solution, the yield of 3,4- dihydroxy-2,5-hexanediones are 90.4%.
(3) 4g member the purification of 3,4- dihydroxy -2,5- acetyl butyryl: is added in 3,4- dihydroxy -2,5- acetyl butyryl solution
Bright powder and 1g sodium chloride, are centrifuged, recycling in zinc powder, iron powder and the manganese powder return step (2) isolated, separation
Liquid phase out is added acetate extractant and is extracted, and extraction carries out acquisition extraction solution in second level extraction tower, with laggard
Row oil is mutually concentrated by evaporation, and recycles ethyl acetate and distilled water, obtains extraction concentrate；After freezing and crystallizing, centrifuge separation is obtained
Obtain 3,4- dihydroxy-2,5-hexanedione mother liquor and 3, the 4- dihydroxy-2,5-hexanedione by purification, 3,4- dihydroxy -2,5-
The purity of acetyl butyryl is 99.91%.
(4) preparation of furanone semi-finished product: 50mL second is added in the 3,4- dihydroxy -2,5- acetyl butyryl 10g after purification of learning from else's experience
Acid butyl ester, 50mL water, 2.7g sodium dihydrogen phosphate, 2g sodium hydroxide pass through 12 hours cyclizations, fully reacting at 80 DEG C
Afterwards, after standing a period of time, fuel-displaced phase and water phase are separated；The water phase returns to cyclisation instead by concentration and recovery sodium dihydrogen phosphate
It answers, and waste water is discharged；The oil mutually passes through concentration and recovery butyl acetate, and obtains liquid phase furanone semi-finished product.
(5) liquid phase furanone semi-finished product the preparation of finished product furanone: are obtained into crude product furan by freezing and crystallizing, centrifuge separation
It mutters ketone, crude product furanone is dissolved into 30mL ethyl alcohol and 45mL ethyl acetate extracts, after filtering out impurity, carry out cold
Freeze brilliant, centrifuge separation and obtain furanone finished product, wet furanone finished product is dried, finished product furanone is obtained, obtains furans
The purity of ketone is 99.93%.
Embodiment 3:
(1) preparation of pyroracemic aldehyde solution: 5g silver catalyst is added in oxidator, then 1,2-PD is added to oxidator
In, it is passed through air, is heated to 380 DEG C, catalytic oxidation is carried out and generates pyroracemic aldehyde, then absorbing acquisition mass concentration through water is
25% pyroracemic aldehyde solution, it is spare.
(2) preparation of 3,4- dihydroxy -2,5- acetyl butyryl solution: it be furnished with thermometer, constant pressure funnel, mechanical stirring
In the four-hole boiling flask of device and gas-guide tube, 50mL pure water, 15g calcium acetate and 1g tetrabutylammonium iodide is added, adds after stirring and dissolving
Enter 5g zinc powder, 2g iron powder and 1g manganese powder, be added dropwise 40mL mass concentration 25% pyroracemic aldehyde aqueous solution and 15mL concentration 50% it is dilute
Sulfuric acid is added dropwise 20 DEG C of process control temp, adds 5g zinc powder, 2g iron powder and 1g manganese powder, then 40mL concentration 25% is added dropwise simultaneously
Pyroracemic aldehyde aqueous solution and 15mL concentration 50% dilute sulfuric acid, be warming up to after dripping 35 DEG C keep the temperature 2 hours, obtain 3,4- dihydroxy
Base -2,5- acetyl butyryl solution, the yield of 3,4- dihydroxy-2,5-hexanediones are 87.4%.
(3) 2g member the purification of 3,4- dihydroxy -2,5- acetyl butyryl: is added in 3,4- dihydroxy -2,5- acetyl butyryl solution
Bright powder and 3g sodium chloride, are centrifuged, recycling in zinc powder, iron powder and the manganese powder return step (2) isolated, separation
Liquid phase out is added acetate extractant and is extracted, and extraction carries out acquisition extraction solution in second level extraction tower, with laggard
Row oil is mutually concentrated by evaporation, and recycles ethyl acetate and distilled water, obtains extraction concentrate；After freezing and crystallizing, centrifuge separation is obtained
Obtain 3,4- dihydroxy-2,5-hexanedione mother liquor and 3, the 4- dihydroxy-2,5-hexanedione by purification, 3,4- dihydroxy -2,5-
The purity of acetyl butyryl is 99.98%.
(4) preparation of furanone semi-finished product: 50mL second is added in the 3,4- dihydroxy -2,5- acetyl butyryl 10g after purification of learning from else's experience
Acid butyl ester, 50mL water, 2.7g sodium dihydrogen phosphate, 2g sodium hydroxide pass through 12 hours cyclizations, fully reacting at 80 DEG C
Afterwards, after standing a period of time, fuel-displaced phase and water phase are separated；The water phase returns to cyclisation instead by concentration and recovery sodium dihydrogen phosphate
It answers, and waste water is discharged；The oil mutually passes through concentration and recovery butyl acetate, and obtains liquid phase furanone semi-finished product.
(5) liquid phase furanone semi-finished product the preparation of finished product furanone: are obtained into crude product furan by freezing and crystallizing, centrifuge separation
It mutters ketone, crude product furanone is dissolved into 35mL ethyl alcohol and 40mL ethyl acetate extracts, after filtering out impurity, carry out cold
Freeze brilliant, centrifuge separation and obtain furanone finished product, wet furanone finished product is dried, finished product furanone is obtained, obtains furans
The purity of ketone is 99.97%.
Comparative example 1: unlike the first embodiment, step is added without iron powder and manganese powder in (2), other steps are identical, obtains
The yield of 3,4- dihydroxy-2,5-hexanediones is 56.4%, furanone gross production rate 50.7%.
Comparative example 2: unlike the first embodiment, being added without iron powder and manganese powder in step (2), at the same zinc powder twice plus
Entering amount is 8g, other steps are identical, and the yield for obtaining 3,4- dihydroxy-2,5-hexanedione is 57.5%, furanone gross production rate
51.7%。
Comparative example 3: unlike the first embodiment, step is added without zinc powder and manganese powder in (2), other steps are identical, obtains
The yield of 3,4- dihydroxy-2,5-hexanediones is 55.4%, furanone gross production rate 49.8%.
Comparative example 4: unlike the first embodiment, step is added without zinc powder and iron powder in (2), other steps are identical, obtains
The yield of 3,4- dihydroxy-2,5-hexanediones is 46.4%, furanone gross production rate 41.7%.
Comparative example 5: unlike the first embodiment, step is added without manganese powder in (2), other steps are identical, obtains 3,4- bis-
The yield of hydroxyl -2,5- acetyl butyryl is 59.4%, furanone gross production rate 53.4%.
Comparative example 6: unlike the first embodiment, step is added without zinc powder in (2), other steps are identical, obtains 3,4- bis-
The yield of hydroxyl -2,5- acetyl butyryl is 63.4%, furanone gross production rate 57%.
Comparative example 7: unlike the first embodiment, step is added without iron powder in (2), other steps are identical, obtains 3,4- bis-
The yield of hydroxyl -2,5- acetyl butyryl is 65.4%, furanone gross production rate 58.8%.
By embodiment 1 and comparative example 1-7 it is found that catalyst can using three kinds of zinc powder, iron powder and manganese powder composite catalysts
It is obviously improved the yield of 3,4- dihydroxy-2,5-hexanedione and the yield of furanone, is obviously improved compared with comparative example 1-7, by reality
Applying a 1-3 can be seen that, using three kinds of zinc powder, iron powder and manganese powder composite catalysts, the mass ratio of zinc powder, iron powder and manganese powder is (3-
5): (2-3): when (1:3), the yield of 3,4- dihydroxy-2,5-hexanediones can reach 87% or more, and use zinc powder, iron powder and
Two kinds or a kind of of catalyst in manganese powder, the yield of 3,4- dihydroxy-2,5-hexanediones is all 66% hereinafter, composite catalyst zinc
Powder, iron powder and manganese powder play synergistic effect, can be obviously improved the yield and furanone of 3,4- dihydroxy-2,5-hexanedione
Gross production rate.
Comparative example 8: as different from Example 2, step is added without anhydrous sodium sulphate and sodium chloride in (3), other steps are identical,
The purity of 3,4- dihydroxy -2,5- acetyl butyryl is 98.43%.
Comparative example 9: as different from Example 2, step is added without sodium chloride in (3), other steps are identical, 3,4- dihydroxies
The purity of base -2,5- acetyl butyryl is 98.56%.
Comparative example 10: as different from Example 2, step is added without anhydrous sodium sulphate in (3), other steps are identical, and 3,4- bis-
The purity of hydroxyl -2,5- acetyl butyryl is 98.34%.
By embodiment 2 and comparative example 8-10 it is found that can obviously be mentioned by addition anhydrous sodium sulphate and sodium chloride in step (3)
The purity of high 3,4- dihydroxy-2,5-hexanedione is in the mass ratio of anhydrous sodium sulphate and sodium chloride it can be seen from embodiment 1-3
(2-4): when (1-3), the purity of 3,4- dihydroxy-2,5-hexanediones is 99.91% or more, without the use of anhydrous sodium sulphate and chlorination
Sodium, or one kind is used alone, the purity of the dihydroxy-2,5-hexanedione arrived is 99% hereinafter, pass through addition anhydrous sodium sulphate and chlorine
Change sodium, plays synergistic effect, can be improved the purity of 3,4- dihydroxy-2,5-hexanedione.
Comparative example 11: as different from Example 3, step is added without ethyl alcohol in (5), other steps are identical, furanone
Purity is 99.53%.
Comparative example 12: as different from Example 3, being added 50mL ethyl alcohol and 25mL in step (5), other steps are identical,
The purity of furanone is 97.56%.
It, can by embodiment 3 and comparative example 11-12 it is found that by combination extractant ethyl alcohol and ethyl acetate in step (5)
The purity for significantly improving furanone, it can be seen from embodiment 1-3 the volume ratio of ethyl alcohol and ethyl acetate be 1:(1.1-2)
When, the purity of furanone is 99.93% or more, when being more than 2:1 without the use of the volume ratio of ethyl alcohol or ethyl alcohol and ethyl acetate,
The purity of its furanone arrived is below 98%.
The above is only exemplary embodiment of the present invention, are not intended to restrict the invention, all in spirit of the invention
With any modifications, equivalent replacements, and improvements made within principle etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of furanone, which is characterized in that include the following steps,
(1) preparation of pyroracemic aldehyde solution: silver catalyst is added in oxidator, then 1,2-PD is added to oxidator
In, it is passed through air, is heated to 360-380 DEG C, catalytic oxidation is carried out and generates pyroracemic aldehyde, it is dense then to absorb acquisition quality through water
Degree is pyroracemic aldehyde solution, spare；
(2) preparation of 3,4- dihydroxy -2,5- acetyl butyryl solution: it be furnished with thermometer, constant pressure funnel, mechanical stirring device
In the four-hole boiling flask of gas-guide tube, 45-55mL pure water, 10-20g sodium acetate and 1-2g tetrabutylammonium iodide, stirring and dissolving is added
Zinc powder, iron powder and manganese powder are added afterwards, 35-45mL pyroracemic aldehyde aqueous solution and 10-20mL dilute sulfuric acid is added dropwise, process control temp is added dropwise
It is 15-25 DEG C, adds zinc powder, iron powder and manganese powder, then 35-45mL pyroracemic aldehyde aqueous solution and 10-20mL dilute sulfuric acid is added dropwise simultaneously,
It is warming up to 30-45 DEG C of heat preservation 1-4 hours after dripping, obtains 3,4- dihydroxy-2,5-hexanedione solution, 3,4- dihydroxy -2,
The yield of 5- acetyl butyryl is 73% or more；
(3) purification of 3,4- dihydroxy -2,5- acetyl butyryl: in 3,4- dihydroxy -2,5- acetyl butyryl solution be added anhydrous sodium sulphate and
Sodium chloride is centrifuged, recycling, the liquid phase isolated in zinc powder, iron powder and the manganese powder return step (2) isolated
Acetate extractant is added to be extracted, extraction carries out acquisition extraction solution in second level extraction tower, then carries out oil and mutually steams
Hair concentration, recycles ethyl acetate and distilled water, obtains extraction concentrate；After freezing and crystallizing, centrifuge separation obtains 3,4- bis-
Hydroxyl -2,5- acetyl butyryl mother liquor and the 3,4- dihydroxy -2,5- acetyl butyryl by purifying；
(4) preparation of furanone semi-finished product: butyl acetate, water, phosphorus is added in the 3,4- dihydroxy -2,5- acetyl butyryl after purification of learning from else's experience
Acid dihydride sodium, sodium hydroxide pass through 10-14 hours cyclizations at 70-90 DEG C, after fully reacting, after standing a period of time,
Separate fuel-displaced phase and water phase；The water phase returns to cyclization by concentration and recovery sodium dihydrogen phosphate, and waste water is discharged；The oil
Mutually pass through concentration and recovery butyl acetate, and obtains liquid phase furanone semi-finished product；
(5) liquid phase furanone semi-finished product the preparation of finished product furanone: are obtained into crude product furans by freezing and crystallizing, centrifuge separation
Crude product furanone is dissolved into ethyl alcohol and ethyl acetate extracts by ketone, and the volume ratio of ethyl alcohol and ethyl acetate is 1:(1.1-
2), after filtering out impurity, freezing and crystallizing, centrifuge separation acquisition furanone finished product is carried out, wet furanone finished product is dried
It is dry, obtain finished product furanone.
2. a kind of preparation method of furanone according to claim 1, it is characterised in that: the step (1) and step (2)
The mass concentration of middle pyroracemic aldehyde solution is 20%-30%.
3. a kind of preparation method of furanone according to claim 1 to 2, it is characterised in that: dilute sulphur in the step (2)
The mass concentration of acid is 30%-50%.
4. a kind of preparation method of furanone according to claim 1 to 3, it is characterised in that: zinc powder in the step (2),
The mass ratio of iron powder and manganese powder is (3-5): (2-3): (1:3).
5. a kind of preparation method of furanone described in -4 according to claim 1, it is characterised in that: acetic acid in the step (2)
Salt is sodium acetate, potassium acetate, zinc acetate, lithium acetate, one or more in calcium acetate.
6. a kind of preparation method of furanone described in -5 according to claim 1, it is characterised in that: be added dropwise in the step (2)
Process control temp is 20 DEG C.
7. a kind of preparation method of furanone described in -6 according to claim 1, it is characterised in that: be added dropwise in the step (2)
It is warming up to 35 DEG C after complete and keeps the temperature 2 hours.
8. a kind of preparation method of furanone described in -7 according to claim 1, it is characterised in that: member is bright in the step (3)
The mass ratio of powder and sodium chloride is (2-4): (1-3).
9. a kind of preparation method of furanone described in -8 according to claim 1, it is characterised in that: cyclisation in the step (4)
Reaction temperature is 80 DEG C.
10. a kind of preparation method of furanone described in -9 according to claim 1, it is characterised in that: cyclisation in the step (4)
Reaction time is 12h.
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