CN105712858A - Method for catalyzing olefin oxidation to produce aromatic aldehyde with metalloporphyrin as catalyst - Google Patents
Method for catalyzing olefin oxidation to produce aromatic aldehyde with metalloporphyrin as catalyst Download PDFInfo
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- CN105712858A CN105712858A CN201410729175.6A CN201410729175A CN105712858A CN 105712858 A CN105712858 A CN 105712858A CN 201410729175 A CN201410729175 A CN 201410729175A CN 105712858 A CN105712858 A CN 105712858A
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Abstract
The invention discloses a method for catalyzing olefin oxidation to produce aromatic aldehyde with metalloporphyrin as a catalyst, wherein the method comprises the steps of with an acetonitrile solvent as a reaction medium, at the reaction temperature of 0-60 DEG C, in the presence of the metalloporphyrin MOF catalyst, with iodosylbenzene as an oxidizing agent, carrying out a stirring reaction of olefin for 0.5-48 h, and directly producing aromatic aldehyde; the metalloporphyrin MOF catalyst is prepared by the steps of carrying out a stirring reaction of cobalt chloride and 5,10,15,20-tetra(4-carboxyphenyl)metalloporphyrin for 12-96 h in a mixed solvent and under a condition of the temperature of 40-150 DEG C, then washing, dipping in ethanol, separating, and carrying out vacuum drying to obtain the metalloporphyrin MOF catalyst. The method has the advantages of simple catalyst preparation and easy separation and recovery, the catalyst system has mild reaction conditions and is efficient and environmentally friendly, and the conversion rate is high.
Description
Technical field
The invention belongs to olefin oxidation and generate aromatic aldehyde field, be specifically related to a kind of metalloporphyrin and do the method that catalyst olefin oxidation generates aromatic aldehyde.
Background technology
Hyacinthin is one of important source material of multiple bouquet type composition synthesis, is also the important intermediate of synthesis agricultural chemicals, spice and artificial sweetener etc., occupies an important position in organic synthesis and chemical industry.At present, the general industrial process of hyacinthin is oxidized with phenethanol or by ethyl phenylacetate through reduction preparation, but these commercial run costs of material are high, complex manufacturing, severe reaction conditions, and the productivity of hyacinthin is low, and purity is not high.The direct catalysis of isomerization Styryl oxide obtains the productivity height of hyacinthin, purity height, and reaction condition is gentle, but the method catalyst service efficiency is low, consumes the chemical reagent of costliness, there is contaminated wastewater, do not meet environmental requirement in course of reaction.And along with the continuous expansion of hyacinthin range of application, the yield of hyacinthin will can not meet far away the demand in market.
Styrene direct oxidation under catalyst action can occur rearrangement reaction to generate hyacinthin, and this reaction is simple and efficient, and hyacinthin productivity is high, purity is good, it is not necessary to purifies further and can apply, therefore progressively obtains attention.At present, industrial with the styrene of low cost for Material synthesis hyacinthin, it is be hydrogenated into phenethanol through Styryl oxide, it is dehydrogenated to hyacinthin again, Styryl oxide industrially mainly adopts the synthesis of halogenohydrin method, and halogenohydrin method method is simple and direct, but material consumption and energy consumption are all significantly high, and seriously polluted, it is urgency production technology to be modified.
Development along with green chemical concept, bionic catalysis synthesis is subject to the favor of scientific research personnel, this method is not only environmentally friendly, and productivity is high, most important is that by-product can reclaim, recycle, the further investigation of this method is not only had important theory value, and has broad application prospects.In the research of bionic catalysis oxyalkylene, metalloporphyrin has great importance, and this kind of catalyst action mild condition, its high efficiency and the feature of environmental protection have enjoyed the concern of Chinese scholars.Equipment is not had any corrosiveness by this type of homogeneous catalysis system, seldom causes environment pollution.Report application Noble Metal Rhodium porphyrin Direct Catalytic Oxidation styrene when 60 DEG C such as Zhi Zhiming, the productivity of hyacinthin is up to 99%.After through improving the cheap and easily-available metallic iron porphyrin Direct Catalytic Oxidation styrene of application, when room temperature, 8h conversion ratio can reach 100%, and hyacinthin selectivity reaches 62%.But regrettably: metalloporphyrin is relatively low due to synthesis yield, price comparison is expensive, therefore, homogeneous catalysis system can make catalysis of metalloporphyrin agent reclaim and recycling difficulty.
The effective way solving the problems referred to above is to manage metalloporphyrin is formed heterogeneous catalysis system: so can strengthen the stability of metalloporphyrin and keep even improving its efficient catalysis activity, easily separates with product again and effectively reuse.At present, porphyrin metal organic framework material is to realize one of Immobilized homogenous catalyst means, and its special construction makes metalloporphyrin be connected by metal ion to exist with single molecule level, separate each other, it is to avoid dimerization, can improve stability and catalysis activity.Meanwhile, its uniform aperture and regular pore passage structure, provide good shape selective for catalytic reaction again.
Summary of the invention
The conversion per pass that it is an object of the invention to exist in aromatic aldehyde technique to overcome current selective oxidation of olefins to prepare is low, it is big to pollute, unit mass metalloporphyrin repeat usage is low not enough problem, for this, the invention provides a kind of metalloporphyrin and do the method that catalyst olefin oxidation generates aromatic aldehyde, specifically provide a kind of homemade catalysis of metalloporphyrin agent, and with iodosobenzene for oxidant, catalytic olefin oxidations prepares aromatic aldehyde.
The technical scheme is that
With acetonitrile solvent for reaction medium, reaction temperature is at 0～60 DEG C, and alkene is under metalloporphyrin MOF catalyst exists, with iodosobenzene for oxidant, and stirring reaction 0.5～48h, directly generate aromatic aldehyde；
Described metalloporphyrin MOF catalyst is by cobaltous chloride and 5,10,15,20-tetra-(4-carboxyl phenyl) metalloporphyrin is in mixed solvent, under 40～150 DEG C of conditions, and stirring reaction 12～96h, by reactant liquor organic solvent washing three times, impregnating 48h in ethanol, separate, vacuum drying obtains metalloporphyrin MOF catalyst.
Iodosobenzene: olefin molar ratio is 0.2～5: 1, iodosobenzene: alkene preferred molar ratio is 0.3～3: 1.
Reaction temperature is preferably 20～35 DEG C；Response time is preferably 4～12h.
Alkene is styrene, p-methylstyrene or to the one in methoxy styrene.
Acetonitrile mass percent in reaction solution is 95-99%.
5,10,15,20-tetra-(4-carboxyl phenyl) metalloporphyrin and cobaltous chloride mol ratio are 1: 1～4, it is preferred to 1: 2～3.
In metalloporphyrin MOF catalyst process, reaction temperature is preferably 70～90 DEG C；Response time is preferably 48～72h.
In described metalloporphyrin MOF catalyst preparation process, mixed solvent is the mixing of high boiling point reagent, alcohol and acid, high boiling point reagent: alcohol: the volume ratio of acid is 2～5: 1: 1, and high boiling point reagent is dimethyl acetylamide (DMAC), alcohol is isopropanol or isobutanol, and acid is acetic acid or formic acid.
Described 5,10,15,20-tetra-(4-carboxyl phenyl) metalloporphyrin is 5,10,15,20-tetra-(4-carboxyl phenyl) manganoporphyrin.
5,10,15,20-tetra-(4-carboxyl phenyl) metalloporphyrin is 1～15mmol/L in the reaction density prepared in metalloporphyrin MOF catalyst system, it is preferred to 4～10mmol/L.
Present invention technique effect compared with prior art is:
Porphyrin MOF catalyst preparing is simple, productivity is high, and metalloporphyrin consumption is few, cost is low.The metalloporphyrin MOF of preparation is a kind of heterogeneous catalysis, and compared with metalloporphyrin homogeneous catalyst, catalytic performance is greatly improved, and can reclaim and reuse, and has more Practical significance.And prepare in the application of aromatic aldehyde at catalytic olefin oxidations, also there is reaction dissolvent and form simple advantage.
Detailed description of the invention
Embodiment 1
1, porphyrin MOF catalyst preparing
0.020g cobaltous chloride is dissolved in 2mLDMAC, add DMAC and dissolve the 5 of 0.015g, 10,15,20-tetra-(4-carboxyl phenyl) manganoporphyrin, stirring to solid is completely dissolved, wherein 5,10,15, the concentration of 20-tetra-(4-carboxyl phenyl) manganoporphyrin solution is 3～6mmol/L, in DMAC: isopropanol: acetic acid is that 3: 1: 1 ratios add alcohol and acid.The solution stirred is put in airtight politef reactor, it is then placed in baking oven and rises to 90 DEG C, and take out from baking oven after keeping 72h, naturally cool to room temperature, open reactor, by DMAC and washed with dichloromethane three times, separate after ethanol soaks 48h, at 50 DEG C of vacuum drying 24h, it is porphyrin MOF through X ray crystallographic analysis.
2, porphyrin MOF catalytic olefin oxidations prepares aromatic aldehyde
(1) 0.01mmol porphyrin MOF catalyst is put in 25mL reactor, add 0.20mmol styrene and 0.10mmol iodosobenzene in 5mL acetonitrile solvent, stir at 25 DEG C, response time 8h.It is 99.7% that reaction utilizes gas chromatographic detection, hyacinthin conversion ratio after terminating, and selectivity is 63.5%.
(2) reacting liquid filtering, the metalloporphyrin MOF acetonitrile wash three times that will reclaim, add styrene and oxidant, in step (1), be circulated Catalysis experiments under reaction condition.Utilizing gas chromatographic detection, hyacinthin conversion ratio is 99.3%, and selectivity is 62.8%.
Embodiment 2
1, porphyrin MOF catalyst preparing
0.020g cobaltous chloride is dissolved in 2mLDMAC, add DMAC and dissolve the 5 of 0.015g, 10,15,20-tetra-(4-carboxyl phenyl) manganoporphyrin, stirring to solid is completely dissolved, wherein 5,10,15, the concentration of 20-tetra-(4-carboxyl phenyl) manganoporphyrin solution is 3～6mmol/L, in DMAC: isopropanol: acetic acid is that 4: 1: 1 ratios add alcohol and acid.The solution stirred is put in airtight politef reactor, it is then placed in baking oven and rises to 90 DEG C, and take out from baking oven after keeping 72h, naturally cool to room temperature, open reactor, by DMAC and washed with dichloromethane three times, separate after ethanol soaks 48h, at 50 DEG C of vacuum drying 24h, it is porphyrin MOF through X ray crystallographic analysis.
2, porphyrin MOF catalytic olefin oxidations prepares aromatic aldehyde
(1) 0.01mmol porphyrin MOF catalyst is put in 25mL reactor, add 0.20mmol styrene and 0.20mmol iodosobenzene in 5mL acetonitrile solvent, stir at 25 DEG C, response time 8h.It is 91.6% that reaction utilizes gas chromatographic detection, hyacinthin conversion ratio after terminating, and selectivity is 48.6%.
(2) reacting liquid filtering, the metalloporphyrin MOF acetonitrile wash three times that will reclaim, add styrene and oxidant, in step (1), be circulated Catalysis experiments under reaction condition.Utilizing gas chromatographic detection, hyacinthin conversion ratio is 90.0%, and selectivity is 46.9%.
Embodiment 3
1, porphyrin MOF catalyst preparing
0.020g cobaltous chloride is dissolved in 2mLDMAC, add DMAC and dissolve the 5 of 0.020g, 10,15,20-tetra-(4-carboxyl phenyl) manganoporphyrin, stirring to solid is completely dissolved, wherein 5,10,15, the concentration of 20-tetra-(4-carboxyl phenyl) manganoporphyrin solution is 3～6mmol/L, in DMAC: isopropanol: acetic acid is that 4: 1: 1 ratios add alcohol and acid.The solution stirred is put in airtight politef reactor, it is then placed in baking oven and rises to 90 DEG C, and take out from baking oven after keeping 72h, naturally cool to room temperature, open reactor, by DMAC and washed with dichloromethane three times, separate after ethanol soaks 48h, at 50 DEG C of vacuum drying 24h, it is porphyrin MOF through X ray crystallographic analysis.
2, porphyrin MOF catalytic olefin oxidations prepares aromatic aldehyde
(1) 0.01mmol porphyrin MOF catalyst is put in 25mL reactor, add 0.20mmol p-methylstyrene and 0.10mmol iodosobenzene in 5mL acetonitrile solvent, stir at 25 DEG C, response time 8h.It is 99.6% that reaction utilizes gas chromatographic detection, p-tolyl acetaldehyde conversion ratio after terminating, and selectivity is 68.3%.
(2) reacting liquid filtering, the metalloporphyrin MOF acetonitrile wash three times that will reclaim, add p-methylstyrene and oxidant, in step (1), be circulated Catalysis experiments under reaction condition.Utilizing gas chromatographic detection, p-tolyl acetaldehyde conversion ratio is 99.3%, and selectivity is 66.4%.
Embodiment 4
1, porphyrin MOF catalyst preparing
0.020g cobaltous chloride is dissolved in 2mLDMAC, add DMAC and dissolve the 5 of 0.025g, 10,15,20-tetra-(4-carboxyl phenyl) manganoporphyrin, stirring to solid is completely dissolved, wherein 5,10,15, the concentration of 20-tetra-(4-carboxyl phenyl) manganoporphyrin solution is 3～6mmol/L, in DMAC: isopropanol: acetic acid is that 5: 1: 1 ratios add alcohol and acid.The solution stirred is put in airtight politef reactor, it is then placed in baking oven and rises to 90 DEG C, and take out from baking oven after keeping 72h, naturally cool to room temperature, open reactor, by DMAC and washed with dichloromethane three times, separate after ethanol soaks 48h, at 50 DEG C of vacuum drying 24h, it is porphyrin MOF through X ray crystallographic analysis.
2, porphyrin MOF catalytic olefin oxidations prepares aromatic aldehyde
(1) 0.01mmol porphyrin MOF catalyst is put in 25mL reactor, add 0.20mmol to methoxy styrene and 0.10mmol iodosobenzene in 5mL acetonitrile solvent, stir at 25 DEG C, response time 8h.It is 99.8% that reaction utilizes gas chromatographic detection, p-methoxy phenylacetaldehyde conversion ratio after terminating, and selectivity is 64.6%.
(2) reacting liquid filtering, the metalloporphyrin MOF acetonitrile wash three times that will reclaim, add methoxy styrene and oxidant, in step (1), be circulated Catalysis experiments under reaction condition.Utilizing gas chromatographic detection, p-methoxy phenylacetaldehyde conversion ratio is 99.6%, and selectivity is 63.7%.
Claims (10)
1. a metalloporphyrin does the method that catalyst olefin oxidation generates aromatic aldehyde, it is characterized in that: with acetonitrile solvent for reaction medium, reaction temperature is at 0～60 DEG C, alkene is under metalloporphyrin MOF catalyst exists, with iodosobenzene for oxidant, stirring reaction 0.5～48h, directly generates aromatic aldehyde；
Described metalloporphyrin MOF catalyst be by cobaltous chloride and 5,10,15,20-tetra-(4-carboxyl phenyl) metalloporphyrin in mixed solvent, under 40～150 DEG C of conditions, stirring reaction 12～96h, washing, impregnating in ethanol, separate, vacuum drying obtains metalloporphyrin MOF catalyst.
2. method according to claim 1, it is characterised in that: iodosobenzene: olefin molar ratio is 0.2～5: 1, iodosobenzene: alkene preferred molar ratio is 0.3～3: 1.
3. method according to claim 1, it is characterised in that: reaction temperature is preferably 20～35 DEG C；Response time is preferably 4～12h.
4. method according to claim 1, it is characterised in that: alkene is styrene, p-methylstyrene or to the one in methoxy styrene.
5. method according to claim 1, it is characterised in that: acetonitrile mass percent in reaction solution is 95-99%.
6. method according to claim 1, it is characterised in that: 5,10,15,20-tetra-(4-carboxyl phenyl) metalloporphyrin and cobaltous chloride mol ratio are 1: 1～4, it is preferred to 1: 2～3.
7. method according to claim 1, it is characterised in that: in metalloporphyrin MOF catalyst preparation process, reaction temperature is preferably 70～90 DEG C；Response time is preferably 48～72h.
8. method according to claim 1, it is characterized in that: in described metalloporphyrin MOF catalyst preparation process, mixed solvent is the mixing of high boiling point reagent, alcohol and acid, high boiling point reagent: alcohol: the volume ratio of acid is 2～5: 1: 1, high boiling point reagent is dimethyl acetylamide (DMAC), alcohol is isopropanol or isobutanol, and acid is acetic acid or formic acid.
9. method according to claim 1, it is characterised in that: described 5,10,15,20-tetra-(4-carboxyl phenyl) metalloporphyrin is 5,10,15,20-tetra-(4-carboxyl phenyl) manganoporphyrin.
10. method according to claim 1, it is characterised in that: 5,10,15,20-tetra-(4-carboxyl phenyl) metalloporphyrin is 1～15mmol/L in the reaction density prepared in metalloporphyrin MOF catalyst system, it is preferred to 4～10mmol/L.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107433206A (en) * | 2017-09-09 | 2017-12-05 | 中国科学院福建物质结构研究所 | A kind of application in polynary zirconium base porous material, preparation method, the de- chromium of photocatalysis |
| CN110152734A (en) * | 2019-05-15 | 2019-08-23 | 山西师范大学 | A kind of application of Hemin@Zn-MOF material in terms of catalysis oxidation |
| CN112844487A (en) * | 2021-02-20 | 2021-05-28 | 南京工业大学 | Alkali lignin supported metalloporphyrin catalyst and preparation method and application thereof |
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| US20060041121A1 (en) * | 2004-08-17 | 2006-02-23 | Chi-Ming Che | Method for conversion of terminal alkenes to aldehydes using ruthenium(IV) porphyrin catalysts |
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| US20060041121A1 (en) * | 2004-08-17 | 2006-02-23 | Chi-Ming Che | Method for conversion of terminal alkenes to aldehydes using ruthenium(IV) porphyrin catalysts |
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| GUO-QIANG CHEN ET AL: "Selective oxidation of terminal aryl and aliphatic alkenes to aldehydes catalyzed by iron(III) porphyrins with triflate as a counter anion", 《CHEM. COMMUN.》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107433206A (en) * | 2017-09-09 | 2017-12-05 | 中国科学院福建物质结构研究所 | A kind of application in polynary zirconium base porous material, preparation method, the de- chromium of photocatalysis |
| CN107433206B (en) * | 2017-09-09 | 2019-05-28 | 中国科学院福建物质结构研究所 | A kind of polynary zirconium base porous material, preparation method, photocatalysis take off the application in chromium |
| CN110152734A (en) * | 2019-05-15 | 2019-08-23 | 山西师范大学 | A kind of application of Hemin@Zn-MOF material in terms of catalysis oxidation |
| CN112844487A (en) * | 2021-02-20 | 2021-05-28 | 南京工业大学 | Alkali lignin supported metalloporphyrin catalyst and preparation method and application thereof |
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