CN105175368A - Preparation method of 3-furfural product - Google Patents
Preparation method of 3-furfural product Download PDFInfo
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- CN105175368A CN105175368A CN201510614152.5A CN201510614152A CN105175368A CN 105175368 A CN105175368 A CN 105175368A CN 201510614152 A CN201510614152 A CN 201510614152A CN 105175368 A CN105175368 A CN 105175368A
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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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- 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
- C07D307/48—Furfural
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Abstract
The invention discloses a preparation method of a 3-furfural product. A palladium catalyst, a heteropoly acid catalyst and a Lewis acid catalyst are selected and dissolved in a three-neck bottle containing 1 mol/L solvent, and water-bath heating is conducted till the temperature ranges from 40 DEG C to 90 DEG C; alpha, beta-unsaturated carboxylic ester and aliphatic aldehydes are selected and mixed with each other, a mixed solution is dropwise added into a flask, and stirring reflux reaction is conducted at the temperature ranging from 40 DEG C to 90 DEG C; after reaction is completed, an extraction agent is added for separation, 3-furoic acid esters are obtained through reduced pressure distillation, and the 3-furfural product is obtained after a reaction is conducted by adding a reducing agent into the flask. According to the preparation method of the 3-furfural product, the alpha, beta-unsaturated carboxylic ester, the aliphatic aldehydes, the heteropoly acid catalyst and the like which are all frequently-used chemical reagents are adopted, the cost is low, operation is convenient and easy to carry out, bulk production can be conducted, the pollution to the environment is less, and the reaction is environmentally friendly; meanwhile, the 3-furfural product is an intermediate with wide application prospect, and synthesis and applications of down-stream products of the 3-furfural product has the wide application prospect.
Description
Technical field
The invention belongs to the synthesis technical field of the pharmaceutical intermediate of 3-furfural and substituent thereof, be specifically related to a kind of preparation method of 3-chaff aldehyde product.
Background technology
3-furfural, has another name called 3-furtural, and furans lopps intermediate can be used as the intermediates such as volatile oil, makeup, fuel, photosensitizers, sterilant or medicine, and application prospect widely.The method of current existing synthesis furan derivatives is: by 1, the intramolecular cyclization of 4 diketone or be that starting raw material synthesizes with α halogenated ketone with β ketone acid (ester), because the catalyzed reaction of transition metal is widely used in the synthesis such as Furan and its derivatives, heterogeneous ring compound, the shortcoming of these reactions applies special chemical reagent, the precursor not easily obtained or needs more synthesis step.In addition, research report at home for 3-furfural synthetic method is fewer, and the main method of producing 3-furfural is backward and big for environment pollution, for this reason, seek the processing method that a kind of reaction conditions is gentle, environmental protection high yield synthesizes 3-furfural, there is potential huge environment and economy benefit.
Summary of the invention
The object of the invention is Problems existing in the synthetic method for existing 3-chaff aldehyde product, provide that a kind of raw material is cheap and easy to get, synthesis step is few, separating-purifying is easy, the synthetic method of high-quality.
In order to solve the problems of the technologies described above, the present invention realizes in the following manner:
A preparation method for 3-chaff aldehyde product, its concrete processing step and condition as follows:
1) choose the palladium catalyst of 0.01 ~ 0.1 part (being amount of substance mark herein and below), the heteropllyacids catalyzer of 0.01 ~ 0.1 part, the lewis acid catalyst of 0.01 ~ 1 part be dissolved in and be equipped with in there-necked flask that concentration is 1mol/L solvent, and by solvent in heating in water bath to 40 ~ 90 DEG C;
2) α of 1 ~ 5 part is chosen again, beta-unsaturated carboxylic acid ester mixes mutually with the fatty aldehydes of 3 ~ 5 parts, draw mixing solutions and dropwise drop to step 1) in there-necked flask in, remain in 0.5 ~ 5h and dropwise, and then under 40 ~ 90 DEG C of conditions stirring and refluxing reaction 1 ~ 8h;
3) treat step 2) in reaction carry out after, add the extraction agent of 1 ~ 5 part, under 0.40 ~ 0.55 normal atmosphere, 3-furoate class is obtained through underpressure distillation after extracting and separating, in the flask of 3-furoate class, add the reductive agent of 0.5 ~ 3 part, reduction reaction obtains 3-chaff aldehyde product.
α described in the present invention, beta-unsaturated carboxylic acid ester has following structure:
Wherein R
1for groups such as hydrogen base, methyl or ethyls, R
2for the group such as methyl or ethyl, if R
1for hydrogen base, then final product is 3-furfural, if R
1for other bases, then final product is 5 replacement 3-furfurals;
Fatty aldehydes described in the method has following structure:
Wherein R
3for groups such as methyl, ethyl or propyl group.
Further, step 1) described in the kind of palladium catalyst be one or more in palladium carbon, Palladous chloride, Palladous nitrate and palladium; The kind of heteropllyacids catalyzer is one or more in phosphorus molybdenum vanadium heteropolyacid, phospho-molybdic acid heteropolyacid, tungsten vanadium heteropolyacid and tungsten acid heteropolyacid; The kind of lewis acid catalyst is one or more in iron(ic) chloride, cupric chloride, Cerium II Chloride and zinc chloride.
Step 1) described in solvent be one or more in hydrochloric acid, glacial acetic acid, methyl alcohol, ethanol, propionic acid, Virahol, tetrahydrofuran (THF) and pyridine.
Preferably, step 3) described in the kind of extraction agent be one or more of chloroform, methylene dichloride, sherwood oil and ethyl acetate; The kind of reductive agent is one or more of diisobutyl aluminium hydride, red aluminium, sodium borohydride and lithium aluminum hydride.
Compared with prior art, the beneficial effect that the present invention has: the present invention adopts α, beta-unsaturated carboxylic acid ester, fatty aldehydes and heteropolyacid catalyst etc., be conventional chemical reagent, with low cost, easy to operation, can produce in a large number, environmental pollution is little, belongs to environmentally friendly reaction; The 3-chaff aldehyde product provided of the present invention, is the Synthesis and application of the intermediate that a class has wide application prospect, its derived product, possesses application prospect widely simultaneously.
Embodiment
Below in conjunction with specific embodiment, the specific embodiment of the present invention is described in further detail; what be necessary to herein means out is; following examples are only for the invention will be further described; limiting the scope of the invention can not be interpreted as; the person skilled in the art in this field makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belongs to scope.
Embodiment 1
Choose the palladium-carbon catalyst of 0.01 part, the phosphorus molybdenum vanadium heteropolyacid of 0.02 part, the Cerium II Chloride catalyzer of 0.02 part, being dissolved in and 2 parts of concentration are housed is in the hydrochloric acid of 1mol/L and the there-necked flask of methyl alcohol, by system in heating in water bath to 40 ~ 90 DEG C; Choose the methyl acrylate of 1 part and the acetaldehyde mixing of 3 parts again, draw mixed solution and dropwise instill in the catalyzer liquid in there-necked flask, remaining on 1h and dropwise, then stirring and refluxing reaction 3h under 40 ~ 90 DEG C of conditions; After question response carries out, cooling adds 5 parts of chloroforms and 3-furoate class is extracted, and steams chloroform and namely obtain 3-furoate class under decompression; In the flask of 3-furoate class, add 0.5 part of diisobutyl aluminium hydride reduction again obtain 3-chaff aldehyde product.
Embodiment 2
Choose the palladium chloride catalyst of 0.02 part, the phosphorus molybdenum vanadium heteropolyacid of 0.04 part, the Cerium II Chloride catalyzer of 0.04 part, being dissolved in and 3 parts of concentration are housed is in the glacial acetic acid of 1mol/L and the there-necked flask of methyl alcohol, by system heating in water bath to 40 ~ 90 DEG C; Choose the propionic aldehyde mixing of the 2-butylene acetoacetic ester of 1 part and 4 parts again, draw in the catalyzer liquid that this mixed solution dropwise instills in there-necked flask, remain on 3h and dropwise, then stirring and refluxing reaction 4h under 40 ~ 90 DEG C of conditions; After question response carries out, cooling adds 3 parts of methylene dichloride and 3-furoate class is extracted, and steams methylene dichloride and namely obtain 3-furoate class under decompression; In the flask of 3-furoate class, add 2 parts of diisobutyl aluminium hydride reduction again obtain 5 3-chaff aldehyde product replaced.
Embodiment 3
Choose the Palladous nitrate catalyzer of 0.03 part, the phosphorus molybdenum vanadium heteropolyacid of 0.025, the ferric chloride catalyst of 0.05 part, being dissolved in and 3 parts of concentration are housed is in the glacial acetic acid of 1mol/L and the there-necked flask of ethanol, by system heating in water bath to 40 ~ 90 DEG C; Choose the 2-pentenoic acid ethyl ester of 2 parts and the acetaldehyde mixing of 5 parts again, draw this mixed solution and dropwise instill in there-necked flask inner catalyst liquid, remain on 3h and dropwise, then stirring and refluxing reaction 5h under 40 ~ 90 DEG C of conditions; After question response carries out, cooling adds 2 parts of sherwood oils and 3-furoate class is extracted, and steams sherwood oil and namely obtain 3-furoate class under decompression; In flask, add 1 part of Lithium Aluminium Hydride reduction again can obtain 5 3-chaff aldehyde product replaced.
Embodiment 4
Choose the palladium acetate catalyst of 0.02 part, the phospho-molybdic acid heteropolyacid of 0.05 part, the copper chloride catalyst of 0.05 part, being dissolved in and 1 part of concentration is housed is in the glacial acetic acid of 1mol/L and the there-necked flask of Virahol, by system heating in water bath to 40 ~ 90 DEG C; Choose the β-dimethyl-aminoethylmethacrylate of 1 part and the acetaldehyde mixing of 5 parts again, this mixed solution is dropwise instilled in there-necked flask inner catalyst liquid, remain on 2.5h and dropwise, then stirring and refluxing reaction 6h under 40 ~ 90 DEG C of conditions; After question response carries out, cooling adds 2 parts of ethyl acetate and 3-furoate class is extracted, and steams ethyl acetate and namely obtain 3-furoate class under decompression; Add in flask again 1 part of red aluminium reducing 5 replace 3-chaff aldehyde product.
Embodiment 5
Choose the Palladous nitrate catalyzer of 0.02 part, the tungsten acid heteropolyacid of 0.02, the Cerium II Chloride catalyzer of 0.05 part, being dissolved in and 1 part of concentration is housed is in the glacial acetic acid of 1mol/L and the there-necked flask of methyl alcohol, by system heating in water bath to 40 ~ 90 DEG C; Choose the β-dimethyl-aminoethylmethacrylate of 2 parts and the acetaldehyde mixing of 5 parts again, this mixed solution is dropwise instilled in there-necked flask inner catalyst liquid, remain on 2h and dropwise, then stirring and refluxing reaction 6h under 40 ~ 90 DEG C of conditions; After question response carries out, cooling adds 2 parts of ethyl acetate and 3-furoate class is extracted, and steams ethyl acetate and namely obtain 3-furoate class under decompression; Add in flask again 2 parts of red aluminium reducings 5 replace 3-chaff aldehyde product.
Embodiment 6
Choose the Palladous nitrate catalyzer of 0.02 part, the tungsten vanadium heteropolyacid of 0.05 part, the ferric chloride catalyst of 0.02 part, being dissolved in and 1 part of concentration is housed is in the hydrochloric acid of 1mol/L and the there-necked flask of Virahol, by system heating in water bath to 40 ~ 90 DEG C; Then choose the β-dimethyl-aminoethylmethacrylate of 3 parts and the acetaldehyde mixing of 5 parts, this mixed solution is dropwise instilled in there-necked flask inner catalyst liquid, remain on 2.5h and dropwise, then stirring and refluxing reaction 5h under 40 ~ 90 DEG C of conditions; After question response carries out, cooling adds 2 parts of ethyl acetate and 3-furoate class is extracted, and steams ethyl acetate and namely obtain 3-furoate class under decompression; Add in flask again 2 parts of Lithium Aluminium Hydrides reduce to obtain 5 replace 3-chaff aldehyde product.
Embodiment 7
Choose the palladium acetate catalyst of 0.02 part, the tungsten vanadium heteropolyacid of 0.04 part, the Cerium II Chloride catalyzer of 0.02 part, being dissolved in and 1 part of concentration is housed is in the hydrochloric acid of 1mol/L and the there-necked flask of Virahol, by system heating in water bath to 40 ~ 90 DEG C; Then choose the ethyl propenoate of 2 parts, 4 parts propionic aldehyde mixing, this mixed solution is dropwise instilled in flask inner catalyst mixed solution, remains on 3h and dropwise, then under 40 ~ 90 DEG C of conditions stirring and refluxing reaction 8h; After question response carries out, cooling adds 2 parts of chloroforms and 3-furoate class is extracted, and steams chloroform and namely obtain 3-furoate class under decompression; Again with 1.5 parts of red aluminium reducings 5 replace 3-chaff aldehyde product.
Embodiment 8
Choose the palladium chloride catalyst of 0.02 part, the tungsten acid heteropolyacid of 0.05 part, the Cerium II Chloride catalyzer of 0.02 part, being dissolved in and 1 part of concentration is housed is in the hydrochloric acid of 1mol/L and the there-necked flask of methyl alcohol, by system heating in water bath to 40 ~ 90 DEG C; Then choose the ethyl propenoate of 3 parts, 5 parts propionic aldehyde mixing, this mixed solution is dropwise instilled in flask inner catalyst mixed solution, remains on 3h and dropwise, then under 40 ~ 90 DEG C of conditions stirring and refluxing reaction 8h; After question response carries out, cooling adds 2 parts of chloroforms and 3-furoate class is extracted, and steams chloroform and namely obtain 3-furoate class under decompression; Again with 1.5 parts of red aluminium reducings 5 replace 3-chaff aldehyde product.
Claims (5)
1. a preparation method for 3-chaff aldehyde product, is characterized in that: concrete processing step and condition as follows:
1) choose the palladium catalyst of 0.01 ~ 0.1 part, the heteropllyacids catalyzer of 0.01 ~ 0.1 part, the lewis acid catalyst of 0.01 ~ 1 part be dissolved in and be equipped with in there-necked flask that concentration is 1mol/L solvent, and by solvent in heating in water bath to 40 ~ 90 DEG C;
2) α of 1 ~ 5 part is chosen again, beta-unsaturated carboxylic acid ester mixes mutually with the fatty aldehydes of 3 ~ 5 parts, draw mixing solutions and dropwise drop to step 1) in there-necked flask in, remain in 0.5 ~ 5h and dropwise, and then under 40 ~ 90 DEG C of conditions stirring and refluxing reaction 1 ~ 8h;
3) treat step 2) in reaction carry out after, add the extraction agent of 1 ~ 5 part, obtain 3-furoate class through underpressure distillation after extracting and separating, in the flask of 3-furoate class, add the reductive agent of 0.5 ~ 3 part, reduction reaction obtains 3-chaff aldehyde product.
2. the preparation method of a kind of 3-chaff aldehyde product according to claim 1, it is characterized in that: described α, beta-unsaturated carboxylic acid ester has following structure:
Wherein R
1for hydrogen base, methyl or ethyl, R
2for methyl or ethyl;
Described fatty aldehydes has following structure:
Wherein R
3for methyl, ethyl or propyl group.
3. the preparation method of a kind of 3-chaff aldehyde product according to claim 1, is characterized in that: described step 1) in the kind of palladium catalyst be one or more in palladium carbon, Palladous chloride, Palladous nitrate and palladium; The kind of heteropllyacids catalyzer is one or more in phosphorus molybdenum vanadium heteropolyacid, phospho-molybdic acid heteropolyacid, tungsten vanadium heteropolyacid and tungsten acid heteropolyacid; The kind of lewis acid catalyst is one or more in iron(ic) chloride, cupric chloride, Cerium II Chloride and zinc chloride.
4. the preparation method of a kind of 3-chaff aldehyde product according to claim 1, is characterized in that: described step 1) in solvent be one or more in hydrochloric acid, glacial acetic acid, methyl alcohol, ethanol, propionic acid, Virahol, tetrahydrofuran (THF) and pyridine.
5. the preparation method of a kind of 3-chaff aldehyde product according to claim 1, is characterized in that: described step 3) in the kind of extraction agent be one or more of chloroform, methylene dichloride, sherwood oil and ethyl acetate; The kind of reductive agent is one or more of diisobutyl aluminium hydride, red aluminium, sodium borohydride and lithium aluminum hydride.
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| CN201510614152.5A CN105175368B (en) | 2015-09-23 | 2015-09-23 | A kind of preparation method of 3 chaff aldehyde product |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794435A (en) * | 2017-04-28 | 2018-11-13 | 复旦大学 | It is a kind of to be used for the integration catalysis conversion method of biomass Furnan products in ethanol |
| CN114920719A (en) * | 2022-06-25 | 2022-08-19 | 湖南华腾制药有限公司 | Preparation method of 3-furfural |
| WO2024033677A1 (en) | 2022-08-09 | 2024-02-15 | Faculdade De Farmácia Da Universidade De Lisboa | One-pot method for the synthesis of 3-acetamido-furfural from n-acetylglucosamine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4126312A (en) * | 1977-02-01 | 1978-11-21 | Brunswick Corporation | Radio-controlled surface target having a pliable cover |
| CN1035540A (en) * | 1988-03-01 | 1989-09-13 | 陈红星 | Sinterless composite tile |
| US7608727B2 (en) * | 2006-02-23 | 2009-10-27 | Daicel Chemical Industries, Ltd. | Process for the preparation of furan compounds |
-
2015
- 2015-09-23 CN CN201510614152.5A patent/CN105175368B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4126312A (en) * | 1977-02-01 | 1978-11-21 | Brunswick Corporation | Radio-controlled surface target having a pliable cover |
| CN1035540A (en) * | 1988-03-01 | 1989-09-13 | 陈红星 | Sinterless composite tile |
| US7608727B2 (en) * | 2006-02-23 | 2009-10-27 | Daicel Chemical Industries, Ltd. | Process for the preparation of furan compounds |
Non-Patent Citations (1)
| Title |
|---|
| 孙昌俊 等: "《有机化合物合成手册》", 30 November 2011, 化学工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794435A (en) * | 2017-04-28 | 2018-11-13 | 复旦大学 | It is a kind of to be used for the integration catalysis conversion method of biomass Furnan products in ethanol |
| CN108794435B (en) * | 2017-04-28 | 2021-06-04 | 复旦大学 | Integrated catalytic conversion method for biomass furfural compounds in ethanol |
| CN114920719A (en) * | 2022-06-25 | 2022-08-19 | 湖南华腾制药有限公司 | Preparation method of 3-furfural |
| WO2024033677A1 (en) | 2022-08-09 | 2024-02-15 | Faculdade De Farmácia Da Universidade De Lisboa | One-pot method for the synthesis of 3-acetamido-furfural from n-acetylglucosamine |
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