CN102976879A - Supported PtAu catalyst and method for catalytic reduction of olefinic bonds or acetylenic bonds by using same - Google Patents
Supported PtAu catalyst and method for catalytic reduction of olefinic bonds or acetylenic bonds by using same Download PDFInfo
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Abstract
The invention relates to a supported PtAu catalyst and a method for catalytic reduction of olefinic bonds or acetylenic bonds by using same, and belongs to the technical field of heterogeneous catalysis. The supported PtAu catalyst is prepared by taking platinum acetylacetonate and chloroauric acid tetrahydrate as precursors and active carbon as a carrier, putting the two precursors into n-octadecylamine to prepare a bimetal PtAu through reduction, and loading the obtained bimetal PtAu on the active carbon. According to the method for catalytic reduction of the olefinic bonds or acetylenic bonds by using supported PtAu, halogenated aryl hydrocarbon is used as a substrate, the supported PtAu is used as a catalyst, and under a normal pressure hydrogen atmosphere at room temperature, the substrate and the catalyst are placed into an organic solvent to react so as to selectively reduce the olefinic bonds or acetylenic bonds in substrate molecules. The method has the advantages of simple preparation process of the catalyst, mild reaction condition, high catalyst activity, selectivity and stability and the like, so that highly selective reduction of the olefinic bonds or acetylenic bonds in a series of halogenated aryl hydrocarbon molecules.
Description
Technical field
The present invention relates to the preparation of loading type PtAu and the method for catalytic reduction ethylene linkage or acetylene bond thereof, belong to the heterogeneous catalysis technology field.
Background technology
The reduction reaction of unsaturated link(age) (such as ethylene linkage, acetylene bond) is one of emphasis of organic synthesis.As a kind of high reactivity commercial catalysts, Pd/C has been widely used in the reduction of ethylene linkage or acetylene bond.Yet, for the substrate of complicated structure, as when a plurality of reducible groups such as ethylene linkage (or acetylene bond), halogen and carbonyl coexist as in the substrate molecule, use commercial Pd/C to be difficult to realize the selective reduction of ethylene linkage or acetylene bond.Therefore, the high-selectivity reduction of ethylene linkage or acetylene bond has very large challenge in the implementation structure complex substrate.
To this, people have mainly studied following two class catalyst system: the one, and the out-phase system take commercial Pd/C as catalyzer needs the extra compound (Org.Lett.2006 that adds sulfur-bearing (such as diphenyl sulfide) or nitrogenous (such as ammonia, pyridine, 2,2 '-two pyridines etc.), 8,3279-3281; Tetrahedron2006,62,11925-11932), thereby suppress the active chemical reduction selectivity that improves ethylene linkage or acetylene bond of Pd/C by these additives; The 2nd, contain the homogeneous system of precious metals complex catalyzer.For example, take sodium-acetate as hydrogen source, rhodium complex is that the diamines of catalyst precursor, N-sulfonylation is part, aqueous phase can realize ethylene linkage in a series of substrate molecules hydrogen transference hydrogenation (J.Org.Chem.2010,75,2981-2988).And for example, use with the N-heterocycle carbine of large steric hindrance and the complex of iridium of phosphine part, under the room temperature nitrogen atmosphere, can realize ethylene linkage in the halogenated aryl hydrocarbon molecule high-selectivity reduction (Chem.Commun.2011,47,11653-11655).For another example, with Cp
2TiCl
2Be catalyzer, the Zn powder of reductibility is additive, and triethylamine hydrochloride is proton source, can realize ethylene linkage in some chlorinated aromatic hydrocarbons molecules selective reduction (Org.Lett.2010,12,44-47).Yet these systems exist catalyzer and ligand structure complicated difficult with shortcomings such as preparation, less stable, catalyzer or additive usage quantity are larger.
Summary of the invention
The reduction ethylene linkage that the purpose of this invention is to provide that a kind of catalyzer preparation procedure is simple, reaction conditions is gentle, catalyst activity and selectivity and stability is higher or the method for acetylene bond.
Technical scheme of the present invention is as follows:
The method of a kind of loading type PtAu catalytic reduction ethylene linkage or acetylene bond is characterized in that the method carries out as follows:
1) take following structural I, II, III or IV as substrate, take loading type PtAu as catalyzer, under room temperature normal pressure nitrogen atmosphere, place organic solvent to react substrate and catalyzer, wherein the volumetric molar concentration of substrate is 0.01～0.25mol/L, and the volumetric molar concentration of catalyzer is 0.0001～0.0025mol/L;
Described substrate structure formula is as follows,
Wherein:
R
1Be selected from halogen;
R
2Be selected from a kind of in hydrogen, thiazolinyl and the alkynyl;
R
3Be selected from a kind of in hydrogen, carbonyl, carboxyl and the ester group;
R
4Be selected from hydrogen;
2) reacted 4～24 hours under the state that stirs, filtering recovering catalyst filtrate distillation desolventizing is obtained target product, or the post separation obtains target product excessively.
Organic solvent of the present invention adopts a kind of in methyl alcohol, ethanol, tetrahydrofuran (THF) and the ethyl acetate.
Loading type PtAu catalyzer of the present invention is characterized in that this catalyzer prepares as follows:
1) stearylamine is added the thermosetting settled solution as solvent, tensio-active agent and reductive agent;
2) continue to be heated to 120～150 ° of C, then add methyl ethyl diketone platinum and four hydration hydrochloro-auric acids, wherein the concentration of methyl ethyl diketone platinum and four hydration hydrochloro-auric acids is 0.0022～0.0066mol/L;
3) continue to be heated to 180～250 ° of C, stir and be cooled to room temperature after 10～30 minutes, with namely obtaining bimetal PtAu after the washing with alcohol, again the bimetal PtAu that obtains is dispersed in the hexanaphthene;
4) in the hexanaphthene of above-mentioned dispersion bimetal PtAu, add gac, wherein the mass ratio of bimetal PtAu and gac is 1:20～1:50, filter after mixture at room temperature stirred 12h at least, dry after with the hexanaphthene washing to filter residue again, namely obtain loading type PtAu.
The nanocrystalline granularity of above-mentioned loading type PtAu catalyzer is 5～15 nanometers.
The present invention compared with prior art, have the following advantages and the high-lighting effect: the inventive method has that the catalyzer preparation procedure is simple, reaction conditions is gentle, catalyst activity, selectivity and the more high outstanding advantages of stability, avoided the complicated and stable not metal complexes of Structure of need in the existing synthetic route, used commercial Pd/C to need extra sulfur-bearing or the nitrogenous shortcomings such as additive of adding, can realize under mild conditions that the high selectivity of ethylene linkage in the halogenated aryl hydrocarbon molecule or acetylene bond reduces.
Description of drawings
Fig. 1 is the transmission electron microscope picture of loading type PtAu.
Embodiment
Loading type PtAu catalyzer provided by the invention prepares as follows:
1) stearylamine is added the thermosetting settled solution as solvent, tensio-active agent and reductive agent;
2) continue to be heated to 120～150 ° of C, then add methyl ethyl diketone platinum and four hydration hydrochloro-auric acids, wherein the concentration of methyl ethyl diketone platinum and four hydration hydrochloro-auric acids is 0.0022～0.0066mol/L;
3) continue to be heated to 180～250 ° of C, stir and be cooled to room temperature after 10～30 minutes, with namely obtaining bimetal PtAu after the washing with alcohol, again the bimetal PtAu that obtains is dispersed in the hexanaphthene;
4) in the hexanaphthene of above-mentioned dispersion bimetal PtAu, add gac, wherein the mass ratio of bimetal PtAu and gac is 1:20～1:50, filter after mixture at room temperature stirred 12h at least, dry after with the hexanaphthene washing to filter residue again, namely obtain loading type PtAu; The nanocrystalline granularity of loading type PtAu catalyzer is 5～15 nanometers.
The method of loading type PtAu catalytic reduction ethylene linkage provided by the present invention or acetylene bond, it carries out as follows:
1) take following structural I or II or III or IV as substrate, take loading type PtAu as catalyzer, under room temperature normal pressure nitrogen atmosphere, place organic solvent to react substrate and catalyzer, wherein the volumetric molar concentration of substrate is 0.01～0.25mol/L, and the volumetric molar concentration of catalyzer is 0.0001～0.0025mol/L; Described organic solvent is selected from a kind of in methyl alcohol, ethanol, tetrahydrofuran (THF) and the ethyl acetate;
Described substrate structure formula is as follows,
Wherein
R
1Be selected from halogen;
R
2Be selected from a kind of in hydrogen, thiazolinyl and the alkynyl;
R
3Be selected from a kind of in hydrogen, carbonyl, carboxyl and the ester group;
R
4Be selected from hydrogen;
2) reacted 4～24 hours under the state that stirs, filtering recovering catalyst obtains target product to filtrate distillation desolventizing or after crossing the post separation.
The below enumerates embodiment the present invention is further described, but the invention is not restricted to following embodiment, and under the scope of described aim, change is included in the technical scope of the present invention before and after not breaking away from.
Embodiment one
Implementation method: continue to be heated to 120 ° of C after stearylamine added the thermosetting settled solution, then add 0.066mmol methyl ethyl diketone platinum and 0.066mmol four hydration hydrochloro-auric acids, wherein the concentration of methyl ethyl diketone platinum and four hydration hydrochloro-auric acids is 0.0066mol/L.With mixture heating up to 180 ° C, stir and be cooled to room temperature after 10 minutes, with namely obtaining bimetal PtAu after the washing with alcohol, disperse with hexanaphthene.Add gac, wherein the mass ratio of bimetal PtAu and gac is 1:50, filter after mixture is at room temperature stirred 48h, again to filter residue with the hexanaphthene washing after drying, namely obtain loading type PtAu, wherein the grain fineness number of PtAu nanoparticle is 5nm.
Embodiment two
Implementation method: stearylamine is added the thermosetting settled solution as solvent, tensio-active agent and reductive agent.Continue to be heated to 140 ° of C, then add methyl ethyl diketone platinum and four hydration hydrochloro-auric acids, wherein the concentration of methyl ethyl diketone platinum and four hydration hydrochloro-auric acids is 0.0022mol/L.Continue to be heated to 230 ° of C, stir and be cooled to room temperature after 20 minutes, with namely obtaining bimetal PtAu after the washing with alcohol, be dispersed in the hexanaphthene.Then add gac, wherein the mass ratio of bimetal PtAu and gac is 1:20, filters after mixture is at room temperature stirred 12h, and is dry after with the hexanaphthene washing to filter residue again, namely obtains loading type PtAu, and wherein the grain fineness number of PtAu nanoparticle is 9nm.
Embodiment three
Implementation method: stearylamine is added the thermosetting settled solution as solvent, tensio-active agent and reductive agent.Continue to be heated to 150 ° of C, then add methyl ethyl diketone platinum and four hydration hydrochloro-auric acids, wherein the concentration of methyl ethyl diketone platinum and four hydration hydrochloro-auric acids is 0.0044mol/L.Continue to be heated to 250 ° of C, stir and be cooled to room temperature after 30 minutes, with namely obtaining bimetal PtAu after the washing with alcohol, be dispersed in the hexanaphthene.Add gac, wherein the mass ratio of bimetal PtAu and gac is 1:40, filter after mixture is at room temperature stirred 24h, again to filter residue with the hexanaphthene washing after drying, namely obtain loading type PtAu, wherein the grain fineness number of PtAu nanoparticle is 15nm.
Embodiment four
Implementation method: at normal temperatures, 2-bromstyrol and loading type PtAu are placed methyl alcohol, wherein the volumetric molar concentration of substrate is 0.10mol/L, and the volumetric molar concentration of catalyzer is 0.0012mol/L.The airtight rear adding of reactor is full of the balloon of hydrogen, takes a breath continuously 3 times, under the state that stirs, mixture is reacted 4h at normal temperatures, filtering recovering catalyst carries out gas chromatography-mass spectrometry analysis to filtrate, and productive rate is 86%.
Embodiment five
Implementation method: at normal temperatures, 3-bromstyrol and loading type PtAu are placed ethyl acetate, wherein the volumetric molar concentration of substrate is 0.15mol/L, and the volumetric molar concentration of catalyzer is 0.0009mol/L.The airtight rear adding of reactor is full of the balloon of hydrogen, takes a breath continuously 3 times, under the state that stirs, mixture is reacted 8h at normal temperatures, filtering recovering catalyst, through gas chromatography-mass spectrometry analysis, productive rate is 95% to filtrate.
Embodiment six
Implementation method: at normal temperatures, 4-bromstyrol and loading type PtAu are placed methyl alcohol, wherein the volumetric molar concentration of substrate is 0.15mol/L, and the volumetric molar concentration of catalyzer is 0.0008mol/L.The airtight rear adding of reactor is full of the balloon of hydrogen, takes a breath continuously 3 times, under the state that stirs, mixture is reacted 12h at normal temperatures, filtering recovering catalyst, through gas chromatography-mass spectrometry analysis, productive rate is 98% to filtrate.
Embodiment seven
Implementation method: at normal temperatures, 4-bromobenzene acetylene and loading type PtAu are placed methyl alcohol, wherein the volumetric molar concentration of substrate is 0.10mol/L, and the volumetric molar concentration of catalyzer is 0.0015mol/L.The airtight rear adding of reactor is full of the balloon of hydrogen, takes a breath continuously 3 times, under the state that stirs, mixture is reacted 16h at normal temperatures, filtering recovering catalyst, through gas chromatography-mass spectrometry analysis, productive rate is 92% to filtrate.
Embodiment eight
Implementation method: at normal temperatures, 4-chloro-styrene and loading type PtAu are placed ethyl acetate, wherein the volumetric molar concentration of substrate is 0.20mol/L, and the volumetric molar concentration of catalyzer is 0.0015mol/L.The airtight rear adding of reactor is full of the balloon of hydrogen, takes a breath continuously 3 times, under the state that stirs, mixture is reacted 6h at normal temperatures, filtering recovering catalyst, through gas chromatography-mass spectrometry analysis, productive rate is 99% to filtrate.
Embodiment nine
Implementation method: at normal temperatures, 4-chlorobenzene subunit acetone and loading type PtAu are placed methyl alcohol, wherein the volumetric molar concentration of substrate is 0.13mol/L, and the volumetric molar concentration of catalyzer is 0.0015mol/L.The airtight rear adding of reactor is full of the balloon of hydrogen, takes a breath continuously 3 times, under the state that stirs, mixture is reacted 24h at normal temperatures, filtering recovering catalyst separates and obtains target product crossing post after the filtrate distillation desolventizing, and productive rate is 93%.
Embodiment ten
Implementation method: at normal temperatures, 4-chloro-cinnamic acid methyl esters and loading type PtAu are placed methyl alcohol, wherein the volumetric molar concentration of substrate is 0.25mol/L, and the volumetric molar concentration of catalyzer is 0.0025mol/L.The airtight rear adding of reactor is full of the balloon of hydrogen, takes a breath continuously 3 times, under the state that stirs, mixture is reacted 20h at normal temperatures, filtering recovering catalyst separates and obtains target product crossing post after the filtrate distillation desolventizing, and productive rate is 98%.
Embodiment 11
Implementation method: at normal temperatures, 4-chloro-cinnamic acid and loading type PtAu are placed tetrahydrofuran (THF), wherein the volumetric molar concentration of substrate is 0.05mol/L, and the volumetric molar concentration of catalyzer is 0.0005mol/L.The airtight rear adding of reactor is full of the balloon of hydrogen, takes a breath continuously 3 times, under the state that stirs, mixture is reacted 24h at normal temperatures, filtering recovering catalyst separates and obtains target product crossing post after the filtrate distillation desolventizing, and productive rate is 92%.
Embodiment 12
Implementation method: at normal temperatures, 2,4 dichloro benzene subunit acetone and loading type PtAu are placed methyl alcohol, wherein the volumetric molar concentration of substrate is 0.21mol/L, and the volumetric molar concentration of catalyzer is 0.0021mol/L.The airtight rear adding of reactor is full of the balloon of hydrogen, takes a breath continuously 3 times, under the state that stirs, mixture is reacted 22h at normal temperatures, filtering recovering catalyst separates and obtains target product crossing post after the filtrate distillation desolventizing, and productive rate is 76%.
Embodiment 13
Implementation method: at normal temperatures, with 5-((7-bromo-1H-indol-3-yl) methylene radical)-3-Methylimidazole quinoline-2,4-diketone and loading type PtAu place ethanol, and wherein the volumetric molar concentration of substrate is 0.01mol/L, and the volumetric molar concentration of catalyzer is 0.0001mol/L.The airtight rear adding of reactor is full of the balloon of hydrogen, takes a breath continuously 3 times, under the state that stirs, mixture is reacted 24h at normal temperatures, filtering recovering catalyst separates and obtains target product crossing post after the filtrate distillation desolventizing, and productive rate is 81%.
Embodiment 14
Implementation method: at normal temperatures, with 5-((7-chloro-1H-indol-3-yl) methylene radical)-3-Methylimidazole quinoline-2,4-diketone and loading type PtAu place ethanol, and wherein the volumetric molar concentration of substrate is 0.02mol/L, and the volumetric molar concentration of catalyzer is 0.0002mol/L.The airtight rear adding of reactor is full of the balloon of hydrogen, takes a breath continuously 3 times, under the state that stirs, mixture is reacted 24h at normal temperatures, filtering recovering catalyst separates and obtains target product crossing post after the filtrate distillation desolventizing, and productive rate is 88%.
Embodiment 15
Implementation method: at normal temperatures, trans-4-bromo-benzoic acid-own ester of 3-alkene and loading type PtAu are placed methyl alcohol, wherein the volumetric molar concentration of substrate is 0.15mol/L, and the volumetric molar concentration of catalyzer is 0.0015mol/L.The airtight rear adding of reactor is full of the balloon of hydrogen, takes a breath continuously 3 times, under the state that stirs, mixture is reacted 24h at normal temperatures, filtering recovering catalyst, to obtaining target product after the filtrate distillation desolventizing, productive rate is 99%.
Claims (4)
1. the method for a loading type PtAu catalytic reduction ethylene linkage or acetylene bond is characterized in that the method carries out as follows:
1) take following structural I, II, III or IV as substrate, take loading type PtAu as catalyzer, under room temperature normal pressure nitrogen atmosphere, place organic solvent to react substrate and catalyzer, wherein the volumetric molar concentration of substrate is 0.01～0.25mol/L, and the volumetric molar concentration of catalyzer is 0.0001～0.0025mol/L;
Described substrate structure formula is as follows,
Wherein:
R
1Be selected from halogen;
R
2Be selected from a kind of in hydrogen, thiazolinyl and the alkynyl;
R
3Be selected from a kind of in hydrogen, carbonyl, carboxyl and the ester group;
R
4Be selected from hydrogen;
2) reacted 4～24 hours under the state that stirs, filtering recovering catalyst filtrate distillation desolventizing is obtained target product, or the post separation obtains target product excessively.
2. the method for loading type PtAu catalytic reduction ethylene linkage as claimed in claim 1 or acetylene bond is characterized in that, described organic solvent adopts a kind of in methyl alcohol, ethanol, tetrahydrofuran (THF) and the ethyl acetate.
3. one kind is used for the as claimed in claim 1 loading type PtAu catalyzer of method, it is characterized in that this catalyzer prepares as follows:
1) stearylamine is added the thermosetting settled solution as solvent, tensio-active agent and reductive agent;
2) continue to be heated to 120～150 ° of C, then add methyl ethyl diketone platinum and four hydration hydrochloro-auric acids, wherein the concentration of methyl ethyl diketone platinum and four hydration hydrochloro-auric acids is 0.0022～0.0066mol/L;
3) continue to be heated to 180～250 ° of C, stir and be cooled to room temperature after 10～30 minutes, with namely obtaining bimetal PtAu after the washing with alcohol, again the bimetal PtAu that obtains is dispersed in the hexanaphthene;
4) in the hexanaphthene of above-mentioned dispersion bimetal PtAu, add gac, wherein the mass ratio of bimetal PtAu and gac is 1:20～1:50, filter after mixture at room temperature stirred 12h at least, dry after with the hexanaphthene washing to filter residue again, namely obtain loading type PtAu.
4. loading type PtAu catalyzer as claimed in claim 3 is characterized in that, the nanocrystalline granularity of loading type PtAu catalyzer is 5～15 nanometers.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103706377A (en) * | 2013-12-20 | 2014-04-09 | 清华大学 | Method for preparing platinum-based catalyst for producing isopropanol through acetone hydrogenation |
| CN104926577A (en) * | 2015-05-05 | 2015-09-23 | 大连理工大学 | Preparation method of substituted cis-olefin |
| CN105727943A (en) * | 2016-01-27 | 2016-07-06 | 清华大学 | Method for synthesizing nano three-way catalyst |
| CN110407681A (en) * | 2019-08-12 | 2019-11-05 | 海南大学 | A kind of dehydrogenation zingiberone derivative, preparation method and application |
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| CN1412164A (en) * | 2001-10-09 | 2003-04-23 | 巴斯福股份公司 | Selective catalytic gas-phase hydrogenation method of chain alkyne, dialkene, chain eneyne hydrocarbon and/or polyene |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103706377A (en) * | 2013-12-20 | 2014-04-09 | 清华大学 | Method for preparing platinum-based catalyst for producing isopropanol through acetone hydrogenation |
| CN103706377B (en) * | 2013-12-20 | 2015-12-30 | 清华大学 | A kind of acetone hydrogenation produces the platinum based catalyst preparation method of isopropyl alcohol |
| CN104926577A (en) * | 2015-05-05 | 2015-09-23 | 大连理工大学 | Preparation method of substituted cis-olefin |
| CN105727943A (en) * | 2016-01-27 | 2016-07-06 | 清华大学 | Method for synthesizing nano three-way catalyst |
| CN110407681A (en) * | 2019-08-12 | 2019-11-05 | 海南大学 | A kind of dehydrogenation zingiberone derivative, preparation method and application |
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