CN104262143B - A kind of method of synthesizing alkene ester - Google Patents
A kind of method of synthesizing alkene ester Download PDFInfo
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- CN104262143B CN104262143B CN201410515600.1A CN201410515600A CN104262143B CN 104262143 B CN104262143 B CN 104262143B CN 201410515600 A CN201410515600 A CN 201410515600A CN 104262143 B CN104262143 B CN 104262143B
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- reactant
- alkene ester
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- hydrogen peroxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
- C07C67/42—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of secondary alcohols or ketones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method of synthesizing alkene ester, at temperature of reaction is 0-60 DEG C, with organic diselenide or organic selenous acid for catalyzer, hydrogen peroxide is oxygenant, and in acetonitrile solvent, catalytic oxidation thing alpha, beta-unsaturated ketone, prepares alkene ester.Described reactant concn is 0.1-1mol/l, and described catalyst levels is the 0.5-10mol% of reactant, and described hydrogen peroxide use is the 120-500mol% of reactant.Energy-conserving and environment-protective of the present invention, its raw material is easy to get, and productive rate is high, and reaction conditions is gentle, and reaction preference is high, and Atom economy is high, is more suitable for large-scale commercial production.
Description
Technical field
The present invention relates to the field of chemical synthesis, be specifically related to a kind of method of synthesizing alkene ester.
Background technology
Alkene ester is important organic compound, is widely used in the fields such as organic synthesis, pharmaceutical chemistry, materials chemistry and food chemistry.At present, the method for synthesis alkene ester mainly contains two kinds, and a kind of is by alkynes and the catalytic addition of carboxylic acid or the oxidative coupling of alkene and carboxylic acid; Another kind is the BaeyerVilliger oxidizing reaction by alpha, beta-unsaturated ketone.A kind of front method needs to use metal catalyst, a large amount of parts or additive, selectivity is low, range of application is narrow, therefore, is not best synthetic route.
But about the BaeyerVilliger oxidation of alpha, beta-unsaturated ketone is with the unique report preparing alkene ester, use inorganic peroxy salt to make oxygenant, can generate a large amount of solid waste after reaction, Atom economy is low, is difficult to be applicable to large-scale commercial production.And range of application is narrow, be only limitted to acetic acid synthesized alkene ester.
At present, the method for the synthesis alkene ester that a kind of productive rate is high, Atom economy is high is lacked.
Summary of the invention
The object of the present invention is to provide the method for the synthesis alkene ester that a kind of productive rate is high, Atom economy is high.
Technical scheme of the present invention is as follows: a kind of method of synthesizing alkene ester, at temperature of reaction is 0-60 DEG C, with organic diselenide or organic selenous acid for catalyzer, hydrogen peroxide is oxygenant, in acetonitrile solvent, and catalytic oxidation thing α, alpha, beta-unsaturated ketone, prepares alkene ester.
Further, the starting point concentration of described reactant is 0.1-1mol/l.
Further, the starting point concentration of described reactant is 0.5mol/l.
Further, the consumption of described catalyzer is the 0.5-10mol% of reactant, and the consumption of described hydrogen peroxide is the 120-500mol% of reactant, and described temperature of reaction is 25 DEG C.
Further, the consumption of described catalyzer is the 5mol% of reactant, and the consumption of described hydrogen peroxide is the 400mol% of reactant.
Further, described catalyzer is at least one in organic diselenide or organic selenous acid.
Further, described catalyzer is diphenyl disenenide ether, 4,4 '-difluorodiphenyl base diselenide, 3,3 '-difluorodiphenyl base diselenide, 2,2 '-difluorodiphenyl base diselenide, 3,3 ', 5,5 '-four trifluoromethyl diphenyl disenenide ether, 4,4 '-dimethoxydiphenyl diselenide, 4, at least one in 4 '-two (N, N-dimethyl) diphenyl disenenide ether, two-1-naphthyl diselenides, dibenzyl diselenide, dicyclohexyl diselenide, benzyl selenous acid, cyclohexyl selenous acid, benzene seleninic acid.
Beneficial effect: energy-conserving and environment-protective of the present invention, its raw material is easy to get, and productive rate is high, and reaction conditions is gentle, and reaction preference is high, and Atom economy is high, is more suitable for large-scale commercial production.Raw material of the present invention is prepared by the Aldol condensation of aldehyde ketone with carrying out atom economy.Relative to prior art, the present invention has range of application more widely, is applicable to the synthesis of various carboxylic acid alkene ester, and is not limited only to acetic ester.
Oxidants hydrogen peroxide of the present invention is clean and cheap and easy to get, and catalyzer organic selenium compounds easily reclaims and environmentally safe, and catalyzed oxidation alpha, beta-unsaturated ketone is to prepare alkene ester.By a large amount of catalyst screenings, we overcome the side reaction based on epoxidation reaction of olefines, make BaeyerVilliger oxidation products alkene ester be primary product.
Embodiment
Further specific descriptions will be done by specific embodiment to the present invention below, but can not be interpreted as it is limiting the scope of the present invention.
Embodiment 1
1mmol alpha, beta-unsaturated ketone, 4mmol hydrogen peroxide (30w/w%), 0.05mmol dibenzyl diselenide stir under room temperature (25 DEG C) in 2ml acetonitrile.After 24h, reaction terminates, and use Rotary Evaporators evaporate to dryness, residue analyses chromatographic separation layer by layer with preparing ripple, obtains alkene ester.
The range of application of inspection reaction substrate is the experimental result of the inspection of substrate range of application as table 1.
Table 1
Note: productive rate is isolated yield.From the above results, this reactive applications is in extensive range, is applicable to synthesize various alkene ester.
Embodiment 2
Other condition with embodiment 1, numbering 1.Use the acetonitrile solvent of different volumes, if table 2 is the different experimental result of acetonitrile solvent volume.
Table 2
Note: bracket is outward GC productive rate is isolated yield in bracket.From the above, initial reaction substrate concentration is between 0.1-1mol/l, and wherein with embodiment 1, the initial reaction substrate concentration in numbering 1 is that the effect of the productive rate of 0.5mol/l is best.
Embodiment 3
Other conditions with embodiment 1, numbering 1.Inspection uses the reaction of different catalysts, is the experimental result of the inspection of different catalysts as table 3.
Table 3
| Numbering | Catalyzer | Productive rate (%) Note |
| 1 | - | 0 |
| 2 | (PhS) 2 | 33 |
| 3 | (PhSe) 2 | 71(67) |
| 4 | (PhTe) 2 | 0 |
| 5 | (4-FC 6H 4Se) 2 | 48 |
| 6 | (3-FC 6H 4Se) 2 | 73 |
| 7 | (2-FC 6H 4Se) 2 | 63 |
| 8 | [3,5-(CF 3) 2C 6H 3Se] 2 | 84 |
| 9 | (4-CH 3OC 6H 4Se) 2 | 63 |
| 10 | [4-(CH 3) 2NC 6H 4Se] 2 | 81 |
| 11 | (1-C 10H 8Se) 2 | 67 |
| 12 | SeO 2 | 58 |
| 13 | PhSeBr | 68 |
| 14 | PhSePh | 17 |
| 15 | i-PrSePh | 58 |
| 16 | EtSePh | 0 |
| 17 | (PhCH 2Se) 2(embodiment 1, numbering 1) | 92(85) |
| 18 | (c-C 6H 11Se) 2 | 88 |
| 19 | PhCH 2Se(O)OH | 86 |
| 20 | c-C 6H 11Se(O)OH | 81 |
| 21 | PhSe(O)OH | 65 |
Note: bracket is outward GC productive rate is isolated yield in bracket.From the above results, diselenide and organic selenous acid effect best, and wherein with embodiment 1, the dibenzyl diselenide gained productive rate in numbering 1 is best effect.
Embodiment 4
Other conditions with embodiment 1, numbering 1.Reaction under catalyst testing dibenzyl diselenide different amounts is the experimental result of the inspection of different dibenzyl diselenide consumption as table 4.
Table 4
| Numbering | Dibenzyl diselenide consumption mol% | Productive rate (%) Note |
| 1 | 0.5 | 50 |
| 2 | 1 | 72 |
| 3 | 2 | 81 |
| 4 | 5 (embodiment 1, numberings 1) | 92(85) |
| 5 | 10 | 67 |
Note: bracket is outward GC productive rate is isolated yield in bracket.From the above results, catalyst levels is with embodiment 1, and the 5mol% gained productive rate in numbering 1 is best effect.
Embodiment 5
Other conditions with embodiment 1, numbering 1.Reaction under inspection hydrogen peroxide use is the experimental result of the inspection of different hydrogen peroxide use as table 5.
Table 5
| Numbering | Hydrogen peroxide use mol% | Productive rate (%) Note |
| 1 | 120 | 33 |
| 2 | 150 | 47 |
| 3 | 200 | 65 |
| 4 | 300 | 75 |
| 5 | 400 (embodiment 1, numberings 1) | 92(85) |
| 6 | 500 | 87 |
Note: bracket is outward GC productive rate is isolated yield in bracket.From the above results, hydrogen peroxide use is with embodiment 1, and the 400mol% gained productive rate in numbering 1 is best effect.
Embodiment 6
Other conditions with embodiment 1, numbering 1.Reaction under inspection differing temps.The experimental result of the inspection that table 6 is differential responses temperature.
Table 6
| Numbering | Temperature of reaction (DEG C) | Productive rate (%) |
| 1 | 0 | 76 |
| 2 | 25 | 92(85) |
| 3 | 40 | 90 |
| 4 | 50 | 72 |
| 5 | 60 | 55 |
Note: bracket is outward GC productive rate is isolated yield in bracket.From the above results, temperature of reaction is with embodiment 1, and when the temperature in numbering 1 is 25 DEG C, gained productive rate is best.
Embodiment 7
Other conditions with embodiment 1, numbering 1.By extraction process concentration and recovery catalyzer from aqueous phase, the efficiency that catalyst testing dibenzyl diselenide is recycled, if table 7 is the experimental result of catalyst recovery utilising efficiency.
Table 7
| Numbering | Recovered frequency | Productive rate (%) Note |
| 1 | 1 | 86 |
| 2 | 2 | 79 |
| 3 | 3 | 77 |
| 4 | 4 | 71 |
| 5 | 5 | 62 |
Note: GC productive rate; From the above results, this catalyst stabilization, repeatedly reusable and productive rate reduces less.Because experimental implementation scale is less, use extraction process when reclaiming catalyzer, catalyst loss is comparatively large, so products collection efficiency can decline to some extent.In large-scale commercial production, by underpressure distillation separated product, residue comes into operation again as catalyzer, thus catalyst loss can be made less, can keep active.
More than show and describe ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and application claims protection domain is defined by appending claims, specification sheets and equivalent thereof.
Claims (5)
1. one kind is synthesized the method for alkene ester, it is characterized in that: at temperature of reaction is 0-60 DEG C, with at least one of dibenzyl diselenide, dicyclohexyl diselenide, benzyl selenous acid, cyclohexyl selenous acid for catalyzer, hydrogen peroxide is oxygenant, in acetonitrile solvent, catalytic oxidation thing alpha, beta-unsaturated ketone, prepares alkene ester.
2. the method for synthesis alkene ester according to claim 1, is characterized in that: the starting point concentration of described reactant is 0.1-1mol/l.
3. the method for synthesis alkene ester according to claim 2, is characterized in that: the starting point concentration of described reactant is 0.5mol/l.
4. the method for synthesis alkene ester according to claim 1, is characterized in that: the consumption of described catalyzer is the 0.5-10mol% of reactant, and the consumption of described hydrogen peroxide is the 120-500mol% of reactant, and described temperature of reaction is 25 DEG C.
5. the method for synthesis alkene ester according to claim 4, is characterized in that: the consumption of described catalyzer is the 5mol% of reactant, and the consumption of described hydrogen peroxide is the 400mol% of reactant.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296480A (en) * | 1999-03-11 | 2001-05-23 | 大赛璐化学工业株式会社 | Process for preparation of esters or lactones |
| CN103012133A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for catalytically oxidizing acetophenone |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296480A (en) * | 1999-03-11 | 2001-05-23 | 大赛璐化学工业株式会社 | Process for preparation of esters or lactones |
| CN103012133A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for catalytically oxidizing acetophenone |
Non-Patent Citations (1)
| Title |
|---|
| 固体酸催化剂的合成及其催化Baeyer-Villiger氧化反应研究;牛棱渊;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20120415(第4期);B014-434 * |
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