CN104311404A - Method for producing cinnamyl aldehyde - Google Patents
Method for producing cinnamyl aldehyde Download PDFInfo
- Publication number
- CN104311404A CN104311404A CN201410531893.2A CN201410531893A CN104311404A CN 104311404 A CN104311404 A CN 104311404A CN 201410531893 A CN201410531893 A CN 201410531893A CN 104311404 A CN104311404 A CN 104311404A
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- CN
- China
- Prior art keywords
- phenylacrolein
- production method
- phenyl aldehyde
- acetaldehyde
- reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a method for producing cinnamyl aldehyde. The method comprises the step of directly performing reaction on benzaldehyde, acetaldehyde, ionic liquid catalysts and proper solvents by using a catalytic synthesis system and an intermittent reaction kettle so as to obtain a mixed solvent. The method is less in reaction wastes, easy for treatment and one-step synthesis, good in operation conditions, low in production cost and less in production investment, and has good production practical prospect; the mol conversion rate of the product reaches more than 92 percent.
Description
Technical field
The present invention relates to a kind of production method of phenylacrolein.
Background technology
Phenylacrolein is present in oil of bay at occurring in nature, from oil of bay, extract complicated, and purification technique difficulty is comparatively large, and the sterling phenylacrolein price of natural extract is very high, and easily from condensation and oxidized, belongs to sensitive materials.Therefore, the preparation method of current phenylacrolein adopts industrial preparative method directly to obtain mostly.
The synthetic method of the conventional phenylacrolein aldol condensation mainly under alkaline condition, namely utilizes α-H activity in the basic conditions in acetaldehyde molecule, with phenyl aldehyde generation aldol reaction, after dehydration, obtains phenylacrolein.Have report to utilize 1% sodium hydroxide to make catalyzer, directly synthesis phenylacrolein molar yield can obtain 44%.Utilize the mixing solutions of sodium acetate and sodium hydroxide for medium, same phenyl aldehyde and the acetaldehyde of using synthesizes phenylacrolein, and molar yield can reach 57%.In this synthetic method, in the basic conditions, all very solution is oxidized for phenyl aldehyde, acetaldehyde and product phenylacrolein, causes efficiency of pcr product very low.
Aldol reaction under acidic conditions also has report, and its cardinal principle is the effect of acid proton, and the polarization of C=O bond is strengthened, causes C=O bond to become enol-type structure, addition directly obtains aldol structure then.But apply from practical study, the aldol condensation under acidic conditions is adopted almost not have industrialized example, this is mainly large due to the aldol condensation difficulty under acidic conditions, and the activity of acid catalysis itself is far smaller than base catalysis system, does not therefore get along with always.
But, adopt acidic catalyst system catalyze aldol, significantly can reduce the useless consumption of phenyl aldehyde, acetaldehyde in phenylacrolein process of manufacture, also can reduce the disproportionation of product phenylacrolein, promote the yield of phenylacrolein.Therefore the production technology method developed with mixing acid alkaline catalysts is also had, processing synthesis phenylacrolein.Because acid-base catalysis is large to the control difficulty of reaction system, therefore this technical scheme waits to continue research.
1992, the Ionic liquids technologies that Wikes proposes was that the research and development of ionic liquid subsequently propose technology initial point.Along with this technology progressively research with carry out, the upgrading of many traditional industry technology has had new thinking.Due to designability and the controllability of ionic liquid zwitterion, make the ionic liquid of exploitation have different solvabilities to inorganics, water, organism and polymkeric substance etc., and its acidity can be adjusted to super acid.Therefore utilize this technical scheme, find the mixing soda acid regulation technology be applicable to, for the process for processing of aldol condensation class product provides novel method.
Summary of the invention
The technology of the present invention is the deficiency solving background technology, provides a kind of production technology synthetic method of phenylacrolein of improvement, thoroughly to solve the technical problem occurred in original phenylacrolein production process.
The object of the invention is to realize as follows: a kind of production method of phenylacrolein, by phenyl aldehyde, acetaldehyde, ionic-liquid catalyst and suitable solvent, adopt and catalyze and synthesize system, adopt batch reactor, direct reaction, obtains mixed solvent;
Further prioritization scheme is: the production method of described a kind of phenylacrolein, acetaldehyde and phenyl aldehyde mol ratio 1:1.2-1:1.4, holder series normal temperature normal pressure in reaction process;
Further prioritization scheme is: the production method of described a kind of phenylacrolein, and solvent adopts the mixing solutions of DMF and toluene, the consumption mol ratio 1:1.1-1:1.5 of DMF and toluene;
Further prioritization scheme is: the production method of described a kind of phenylacrolein, and the total mole dosage of mixed solvent is 2.1-4.7 times of phenyl aldehyde mole dosage;
Further prioritization scheme is: the production method of described a kind of phenylacrolein, adds stagnant catalyst by above-mentioned mixing solutions, and its consumption, to add phenyl aldehyde quality, 0.03-0.06%, reacts 3 hours, can obtain high purity phenylacrolein;
Further prioritization scheme is: the production method of described a kind of phenylacrolein, described solid catalyst is: gac 3-5 gram, be dispersed in 200 milliliters of tetrahydrofuran (THF)s, slow dropping mass percentage is the trifluoroacetic acid 1-butyl-3-Methylimidazole aqueous solution 15g of 3%, and Forced Dispersion 2-3 hour.After having disperseed, desolvation.
Advantage of the present invention: the ionic-liquid catalyst catalysis being adsorbed in activated carbon surface that the present invention adopts, under normal temperature and pressure conditions, green syt phenylacrolein, in reaction process, alkalescence is faint, and there is acidic catalyst end, and therefore phenyl aldehyde, acetaldehyde side reaction are few, useless consumption is almost nil, reaction process does not need isolated air or oxygen, and reaction waste is few, and is easy to process, one-step synthesis, operational condition is good, low production cost, and investment of production is few, product molar transformation efficiency reaches more than 92%, has and produces practical prospect preferably.
embodiment:
A production method for phenylacrolein, by phenyl aldehyde, acetaldehyde, ionic-liquid catalyst and suitable solvent, adopt and catalyze and synthesize system, adopt batch reactor, direct reaction, obtains mixed solvent; Acetaldehyde and phenyl aldehyde mol ratio 1:1.2-1:1.4, holder series normal temperature normal pressure in reaction process; Solvent adopts the mixing solutions of DMF and toluene, the consumption mol ratio 1:1.1-1:1.5 of DMF and toluene; The total mole dosage of mixed solvent is 2.1-4.7 times of phenyl aldehyde mole dosage; Above-mentioned mixing solutions is added stagnant catalyst, and its consumption, to add phenyl aldehyde quality, 0.03-0.06%, reacts 3 hours, can obtain high purity phenylacrolein; Described solid catalyst is: gac 3-5 gram, is dispersed in 200 milliliters of tetrahydrofuran (THF)s, slowly drips the trifluoroacetic acid 1-butyl-3-Methylimidazole aqueous solution 15g that mass percentage is 3%, and Forced Dispersion 2-3 hour.After having disperseed, desolvation.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. a production method for phenylacrolein, is characterized in that: by phenyl aldehyde, acetaldehyde, ionic-liquid catalyst and suitable solvent, adopts and catalyzes and synthesizes system, and adopt batch reactor, direct reaction, obtains mixed solvent.
2. the production method of a kind of phenylacrolein according to claim 1, is characterized in that: acetaldehyde and phenyl aldehyde mol ratio 1:1.2-1:1.4, holder series normal temperature normal pressure in reaction process.
3. the production method of a kind of phenylacrolein according to claim 1, is characterized in that: solvent adopts the mixing solutions of DMF and toluene, the consumption mol ratio 1:1.1-1:1.5 of DMF and toluene.
4. the production method of a kind of phenylacrolein according to claim 1, is characterized in that: the total mole dosage of mixed solvent is 2.1-4.7 times of phenyl aldehyde mole dosage.
5. the production method of a kind of phenylacrolein according to claim 1, it is characterized in that: above-mentioned mixing solutions is added stagnant catalyst, its consumption is to add phenyl aldehyde quality, 0.03-0.06%, react 3 hours, high purity phenylacrolein can be obtained.
6. the production method of a kind of phenylacrolein according to claim 5, it is characterized in that: described solid catalyst is: gac 3-5 gram, be dispersed in 200 milliliters of tetrahydrofuran (THF)s, slow dropping mass percentage is the trifluoroacetic acid 1-butyl-3-Methylimidazole aqueous solution 15g of 3%, and Forced Dispersion 2-3 hour, after having disperseed, desolvation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410531893.2A CN104311404A (en) | 2014-10-11 | 2014-10-11 | Method for producing cinnamyl aldehyde |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410531893.2A CN104311404A (en) | 2014-10-11 | 2014-10-11 | Method for producing cinnamyl aldehyde |
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| CN104311404A true CN104311404A (en) | 2015-01-28 |
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| CN201410531893.2A Pending CN104311404A (en) | 2014-10-11 | 2014-10-11 | Method for producing cinnamyl aldehyde |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860805A (en) * | 2015-06-16 | 2015-08-26 | 江苏常州酞青新材料科技有限公司 | Production method for preparing cinnamaldehyde |
| CN105152891A (en) * | 2015-10-22 | 2015-12-16 | 山东国邦药业股份有限公司 | Synthesis method of cinnamaldehyde |
| CN109824490A (en) * | 2019-02-13 | 2019-05-31 | 上海拜乐新材料科技有限公司 | A kind of preparation method of cinnamic acid and its derivative |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0771780A1 (en) * | 1995-11-06 | 1997-05-07 | Dsm N.V. | Method for preparing an alpha-alkylcinnamaldehyde |
| CN101316809A (en) * | 2005-12-01 | 2008-12-03 | 花王株式会社 | Process for producing alpha,beta-unsaturated aldehyde compounds |
| CN102659542A (en) * | 2012-05-02 | 2012-09-12 | 中国科学院过程工程研究所 | Method for preparing methyl acrolein by catalyzing condensation of formaldehyde and propionaldehyde by utilizing ionic liquid |
-
2014
- 2014-10-11 CN CN201410531893.2A patent/CN104311404A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0771780A1 (en) * | 1995-11-06 | 1997-05-07 | Dsm N.V. | Method for preparing an alpha-alkylcinnamaldehyde |
| CN101316809A (en) * | 2005-12-01 | 2008-12-03 | 花王株式会社 | Process for producing alpha,beta-unsaturated aldehyde compounds |
| CN102659542A (en) * | 2012-05-02 | 2012-09-12 | 中国科学院过程工程研究所 | Method for preparing methyl acrolein by catalyzing condensation of formaldehyde and propionaldehyde by utilizing ionic liquid |
Non-Patent Citations (3)
| Title |
|---|
| ABOLGHASEM DAVOODNIA ET AL.: "Solvent-Free Selective Cross-Aldol Condensation of Ketones with Aromatic Aldehydes Efficiently Catalyzed by a Reusable Supported Acidic Ionic Liquid", 《CHINESE JOURNAL OF CATALYSIS》 * |
| 李海花等: "羟醛缩合法合成肉桂醛的工艺研究", 《唐山学院学报》 * |
| 赵地顺等: "离子液体在Aldol 反应中的应用", 《化学试剂》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860805A (en) * | 2015-06-16 | 2015-08-26 | 江苏常州酞青新材料科技有限公司 | Production method for preparing cinnamaldehyde |
| CN105152891A (en) * | 2015-10-22 | 2015-12-16 | 山东国邦药业股份有限公司 | Synthesis method of cinnamaldehyde |
| CN105152891B (en) * | 2015-10-22 | 2018-03-16 | 山东国邦药业股份有限公司 | A kind of synthetic method of cinnamic acid |
| CN109824490A (en) * | 2019-02-13 | 2019-05-31 | 上海拜乐新材料科技有限公司 | A kind of preparation method of cinnamic acid and its derivative |
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Application publication date: 20150128 |