CN104496946A - Method for purifying 2,5-furyldiformaldehyde from dimethyl sulfoxide solution - Google Patents
Method for purifying 2,5-furyldiformaldehyde from dimethyl sulfoxide solution Download PDFInfo
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- CN104496946A CN104496946A CN201410701765.8A CN201410701765A CN104496946A CN 104496946 A CN104496946 A CN 104496946A CN 201410701765 A CN201410701765 A CN 201410701765A CN 104496946 A CN104496946 A CN 104496946A
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- dimethyl sulfoxide
- dff
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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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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Abstract
The invention provides a method for purifying 2,5-furyldiformaldehyde from a dimethyl sulfoxide solution, which comprises the following steps: A. adding distilled water, and stirring to obtain a mixed solution; B. adding dichloromethane, stirring, and standing to stratify; and C. taking the understratum solution, and evaporating to remove the solvent, thereby obtaining the 2,5-furyldiformaldehyde, wherein the volume ratio of the distilled water to the dimethyl sulfoxide solution is (1-10):1, and the volume ratio of the dichloromethane to the mixed solution is (0.2-2):1. The method is simple to operate, and can effectively transfer the 2,5-furyldiformaldehyde in the dimethyl sulfoxide solution into the dichloromethane; and since the dichloromethane has lower boiling point and is easy to remove, the 2,5-furyldiformaldehyde with higher purity can be obtained.
Description
Technical field
The present invention relates to method of purification, more specifically, relate to a kind of method of DFF of purifying from dimethyl sulfoxide solution.
Background technology
DFF is a kind of important furan derivative, is a kind of multiduty organic synthesis intermediate.It can as monomer for the production of polymkeric substance, also can be used for synthetic drugs and intermediate, anti-mycotic agent, macrocyclic ligand etc.At present, 2,5-furans dicarbaldehyde is oxidized obtained usually by 5 hydroxymethyl furfural, but reaction is carried out usually in the dimethylsulfoxide solvent with dehydration and stable intermediate function, and methyl-sulphoxide boiling point is higher, the method according to distillation is separated DFF, DFF can occur to react further with by product and reduce isolated yield.From dimethylsulfoxide solvent, how to isolate DFF become the key issue limiting its scale operation.
Summary of the invention
The present invention, for overcoming at least one defect described in above-mentioned prior art, provides a kind of method of DFF of purifying from dimethyl sulfoxide solution.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
To purify from dimethyl sulfoxide solution the method for DFF, comprise the following steps:
A adds distilled water, stirs, obtains mixing solutions;
B adds methylene dichloride, stirs, static layering;
C takes off a layer solution, and evaporation of solvent obtains DFF;
Described distilled water is 1 ~ 10:1 with the ratio of the volume of described dimethyl sulfoxide solution;
Described methylene dichloride is 0.2 ~ 2:1 with the ratio of the volume of described mixing solutions.
Because the derivative produced in methyl-sulphoxide and reaction process thereof is soluble in water, and 2,5-furans dicarbaldehyde is not soluble in water and be soluble in methylene dichloride, by coordinating of water and methylene dichloride, just can simply 2 in dimethyl sulfoxide solution, 5-furans dicarbaldehyde is transferred in methylene dichloride, and methylene dichloride boiling point is lower, easily removes.
Preferably, it is characterized in that, also comprise step D after step C: by described dissolution of crystals in containing in methylene dichloride/water, stir, static layering, takes off a layer solution, evaporation of solvent; Repeat above step 2 ~ 5 time; Described methylene dichloride is 1 ~ 4:1 with the ratio of the volume of described water.
Preferably, described step B also comprises and adds hexanaphthene; The ratio of the volume of described hexanaphthene and described methylene dichloride is 0 ~ 1:1; Add hexanaphthene and promote that DFF enters organic phase further, further the 5 hydroxymethyl furfural in solution is transferred in the middle of aqueous phase simultaneously.
Preferably, described distilled water is 5:1 with the ratio of the volume of described dimethyl sulfoxide solution.
Preferably, described methylene dichloride is 0.5:1 with the ratio of the volume of described mixing solutions.
Preferably, the churning time in described steps A is 10 ~ 30 min.
Preferably, the churning time in described step B is 20 ~ 40 min.
Preferably, the rest time in described step B is 5 ~ 30 min.
Compared with prior art, the invention has the beneficial effects as follows:
The method of DFF of purifying from dimethyl sulfoxide solution of the present invention, simple to operate, can effectively the DFF in dimethyl sulfoxide solution be transferred in methylene dichloride, methylene dichloride boiling point be lower, easy removing, obtains the DFF that purity is higher.
Embodiment
Below in conjunction with embodiment, invention is further described.These embodiments are only describe typical case of the present invention, but the present invention is not limited thereto.Test method used in following embodiment if no special instructions, is ordinary method, the raw material used, reagent etc., and if no special instructions, being can from raw material that commercial sources obtains and the reagent such as routine is commercial.
embodiment 1
Adopt in this experiment via 5 hydroxymethyl furfural oxidation obtain containing 2, the methyl-sulphoxide reaction soln of 5-furans dicarbaldehyde (is analyzed known through GC, containing 209 mg DFFs in every 2 ml methyl-sulphoxides, the 5 hydroxymethyl furfural that 57 mg unreacteds are complete)
A. add 10 ml distilled water to above-mentioned containing in the dimethyl sulfoxide solution of DFF, stir 20 min, obtain mixing solutions;
B. add 3 ml methylene dichloride, stir 30 min, static 15 min;
C. take off a layer solution, evaporation of solvent, obtain crystal.
With the quality of front DFF of purifying for benchmark, the yield calculating crystal is 95%, and analyze known through GC, the purity of DFF is 89%.
embodiment 2
Adopt in this experiment via 5 hydroxymethyl furfural oxidation obtain containing 2, the methyl-sulphoxide reaction soln of 5-furans dicarbaldehyde (is analyzed known through GC, containing 209 mg DFFs in every 2 ml methyl-sulphoxides, the 5 hydroxymethyl furfural that 57 mg unreacteds are complete)
A. add 2 ml distilled water to above-mentioned containing in the dimethyl sulfoxide solution of DFF, stir 10 min, obtain mixing solutions;
B. add 4ml methylene dichloride, stir 20 min, static 5 min;
C. take off a layer solution, evaporation of solvent, obtain crystal.
With the quality of front DFF of purifying for benchmark, the yield calculating crystal is 96%, and analyze known through GC, the purity of DFF is 85%.
embodiment 3
Adopt in this experiment via 5 hydroxymethyl furfural oxidation obtain containing 2, the methyl-sulphoxide reaction soln of 5-furans dicarbaldehyde (is analyzed known through GC, containing 209 mg DFFs in every 2 ml methyl-sulphoxides, the 5 hydroxymethyl furfural that 57 mg unreacteds are complete)
A. add 20 ml distilled water to above-mentioned containing in the dimethyl sulfoxide solution of DFF, stir 20 min, obtain mixing solutions;
B. add 4ml methylene dichloride, stir 40 min, static 30 min;
C. take off a layer solution, evaporation of solvent, obtain crystal.
With the quality of front DFF of purifying for benchmark, the yield calculating crystal is 96%, and analyze known through GC, the purity of DFF is 88%.
embodiment 4
The methyl-sulphoxide reaction soln (analyzing known through GC, containing 200 mg DFFs in every 2 ml methyl-sulphoxides) containing DFF obtained via 5 hydroxymethyl furfural oxidation is adopted in this experiment,
A. add 20 ml distilled water to above-mentioned containing in the dimethyl sulfoxide solution of DFF, stir 20 min, obtain mixing solutions;
B. add 3 ml methylene dichloride, stir 30 min, static 10 min;
C. take off a layer solution, evaporation of solvent, obtain crystal.
D. be the methylene dichloride/water of 1:1 in volume ratio by above-mentioned dissolution of crystals, stir, static layering, takes off a layer solution, evaporation of solvent; Repeat above step 3 time.
With the quality of front DFF of purifying for benchmark, the yield calculating crystal is 92%, and analyze known through GC, the purity of DFF is 95%.
embodiment 5
The methyl-sulphoxide reaction soln (analyzing known through GC, containing 200 mg DFFs in every 2 ml methyl-sulphoxides) containing DFF obtained via 5 hydroxymethyl furfural oxidation is adopted in this experiment,
A. add 10 ml distilled water to above-mentioned containing in the dimethyl sulfoxide solution of DFF, stir 20 min, obtain mixing solutions;
B. add 6 ml methylene dichloride and 0.6 ml hexanaphthene, stir 30 min, static 15 min;
C. take off a layer solution, evaporation of solvent, obtain crystal.
D. be the methylene dichloride/water of 1:1 in volume ratio by above-mentioned dissolution of crystals, stir, static layering, takes off a layer solution, evaporation of solvent; Repeat above step 3 time.
With the quality of front DFF of purifying for benchmark, the yield calculating crystal is 93%, and analyze known through GC, the purity of DFF is 98%.
embodiment 6
The methyl-sulphoxide reaction soln (analyzing known through GC, containing 200 mg DFFs in every 2 ml methyl-sulphoxides) containing DFF obtained via 5 hydroxymethyl furfural oxidation is adopted in this experiment,
A. add 10 ml distilled water to above-mentioned containing in the dimethyl sulfoxide solution of DFF, stir 20 min, obtain mixing solutions;
B. add 6 ml methylene dichloride and 6 ml hexanaphthenes, stir 30 min, static 15 min;
C. take off a layer solution, evaporation of solvent, obtain crystal.
D. be the methylene dichloride/water of 1:1 in volume ratio by above-mentioned dissolution of crystals, stir, static layering, takes off a layer solution, evaporation of solvent; Repeat above step 3 time.
With the quality of front DFF of purifying for benchmark, the yield calculating crystal is 96%, and analyze known through GC, the purity of DFF is 96%.
embodiment 7
The methyl-sulphoxide reaction soln (analyzing known through GC, containing 200 mg DFFs in every 2 ml methyl-sulphoxides) containing DFF obtained via 5 hydroxymethyl furfural oxidation is adopted in this experiment,
A. add 10 ml distilled water to above-mentioned containing in the dimethyl sulfoxide solution of DFF, stir 20 min, obtain mixing solutions;
B. add 6 ml methylene dichloride and 0.6 ml hexanaphthene, stir 30 min, static 15 min;
C. take off a layer solution, evaporation of solvent, obtain crystal.
D. be the methylene dichloride/water of 1:1 in volume ratio by above-mentioned dissolution of crystals, stir, static layering, takes off a layer solution, evaporation of solvent; Repeat above step 5 time.
With the quality of front DFF of purifying for benchmark, the yield calculating crystal is 94%, and analyze known through GC, the purity of DFF is 99%.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.All any amendments done within the spirit and principles in the present invention, equivalent to replace and improvement etc., within the protection domain that all should be included in the claims in the present invention.
Claims (8)
1. to purify from dimethyl sulfoxide solution the method for DFF, it is characterized in that, comprise the following steps:
A adds distilled water, stirs, obtains mixing solutions;
B adds methylene dichloride, stirs, static layering;
C takes off a layer solution, and evaporation of solvent obtains crystal;
Described distilled water is 1 ~ 10:1 with the ratio of the volume of described dimethyl sulfoxide solution;
Described methylene dichloride is 0.2 ~ 2:1 with the ratio of the volume of described mixing solutions.
2. the method for DFF of purifying from dimethyl sulfoxide solution according to claim 1, is characterized in that, also step D is comprised: by described dissolution of crystals in containing in methylene dichloride/water, stir, static layering after step C, take off a layer solution, evaporation of solvent; Repeat above step 2 ~ 5 time;
Described methylene dichloride is 1 ~ 4:1 with the ratio of the volume of described water.
3. the method for DFF of purifying from dimethyl sulfoxide solution according to claim 1 and 2, it is characterized in that, described step B also comprises and adds hexanaphthene;
The ratio of the volume of described hexanaphthene and described methylene dichloride is 0 ~ 1:1.
4. the method for DFF of purifying from dimethyl sulfoxide solution according to claim 1, is characterized in that, described distilled water is 5:1 with the ratio of the volume of described dimethyl sulfoxide solution.
5. the method for DFF of purifying from dimethyl sulfoxide solution according to claim 1, is characterized in that, described methylene dichloride is 0.5:1 with the ratio of the volume of described mixing solutions.
6. the method for DFF of purifying from dimethyl sulfoxide solution according to claim 1, is characterized in that, the churning time in described steps A is 10 ~ 30 min.
7. the method for DFF of purifying from dimethyl sulfoxide solution according to claim 1, is characterized in that, the churning time in described step B is 20 ~ 40 min.
8. the method for DFF of purifying from dimethyl sulfoxide solution according to claim 1, is characterized in that, the rest time in described step B is 5 ~ 30 min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348236A (en) * | 2015-12-15 | 2016-02-24 | 林康艺 | Method for extracting furan-2,5-dicarbaldehyde by utilizing zinc chloride solution |
| CN105348237A (en) * | 2015-12-15 | 2016-02-24 | 林康艺 | Method for extracting furan-2,5-dicarbaldehyde by utilizing magnesium chloride solution |
| CN105384712A (en) * | 2015-12-15 | 2016-03-09 | 林康艺 | Method for extracting 2, 5-furandicarboxaldehyde by potassium chloride solution |
| CN105439992A (en) * | 2015-12-15 | 2016-03-30 | 林康艺 | Method for extracting furan-2, 5-dicarbaldehyde through sodium chloride solution |
| CN105753819A (en) * | 2016-04-26 | 2016-07-13 | 张玲 | Method for purifying 5-hydroxymethylfurfural |
| CN105884721A (en) * | 2016-04-26 | 2016-08-24 | 张玲 | Method for purifying 2, 5-furan dicarbaldehyde |
-
2014
- 2014-11-28 CN CN201410701765.8A patent/CN104496946A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348236A (en) * | 2015-12-15 | 2016-02-24 | 林康艺 | Method for extracting furan-2,5-dicarbaldehyde by utilizing zinc chloride solution |
| CN105348237A (en) * | 2015-12-15 | 2016-02-24 | 林康艺 | Method for extracting furan-2,5-dicarbaldehyde by utilizing magnesium chloride solution |
| CN105384712A (en) * | 2015-12-15 | 2016-03-09 | 林康艺 | Method for extracting 2, 5-furandicarboxaldehyde by potassium chloride solution |
| CN105439992A (en) * | 2015-12-15 | 2016-03-30 | 林康艺 | Method for extracting furan-2, 5-dicarbaldehyde through sodium chloride solution |
| CN105753819A (en) * | 2016-04-26 | 2016-07-13 | 张玲 | Method for purifying 5-hydroxymethylfurfural |
| CN105884721A (en) * | 2016-04-26 | 2016-08-24 | 张玲 | Method for purifying 2, 5-furan dicarbaldehyde |
| CN105753819B (en) * | 2016-04-26 | 2018-06-08 | 张玲 | A kind of method of 5 hydroxymethyl furfural purifying |
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