CN102658204A - Novel method for synthesizing Wilkinson rhodium catalyst - Google Patents
Novel method for synthesizing Wilkinson rhodium catalyst Download PDFInfo
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- CN102658204A CN102658204A CN2012101073918A CN201210107391A CN102658204A CN 102658204 A CN102658204 A CN 102658204A CN 2012101073918 A CN2012101073918 A CN 2012101073918A CN 201210107391 A CN201210107391 A CN 201210107391A CN 102658204 A CN102658204 A CN 102658204A
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Abstract
The invention discloses a novel method for synthesizing a Wilkinson rhodium catalyst. The novel method is characterized by comprising the following steps of: 1) adding rhodium chloride trihydrate and triphenylphosphine into a three-necked flask at room temperature, simultaneously adding a mixed solvent under the protection of nitrogen, followed by uniform magnetic stirring, heating and refluxing; 2) letting a reaction system gradually turn turbid orange from turbid rose at the beginning, generating claret precipitate, and stopping the reaction; and 3) filtering at room temperature and under protection of nitrogen, repeatedly washing by the use of anhydrous ether, filtering, and drying under vacuum to obtain the Wilkinson rhodium catalyst. The invention has advantages of simple operation, high reaction yield, safe technological process, mild reaction condition and less ''three wastes (waste gas, waste water and industrial residue)'', and has great popularization values and social and economic benefits.
Description
Technical field:
The present invention relates to a kind of new method of synthetic Wilkinson type rhodium catalyst, affiliated field is the new material new method.
Background technology:
Wilkinson type rhodium catalyst is mainly used in transition metal-catalyzed organic reaction research; For example, the part of paraffin catalytic hydrogenation reaction, aldehyde de-carbonyl reaction, propylene replaces priming reaction of oxidation, isomerization, carbonylation, hydrogenation, silicon hydrogenation and c h bond or the like; The product that obtains through the method has been applied to numerous areas such as natural products, chemistry of pesticide, materials chemistry, medicine be synthetic.Wilkinson type rhodium catalyst is used ten minutes extensively, and therefore the more simple synthesis technique of development makes it in industry, obtain very necessity of wider popularization; Simultaneously, Wilkinson type rhodium catalyst is prepared by rhodium trichloride hydrate, so its productive rate of design improvement experimental implementation raising, and then the utilization rate of raising rhodium has important and practical meanings.
Before the present invention provides; The synthesis technique of Wilkinson type rhodium catalyst and operation relative complex: under the inert gas shielding, the triphenyl phosphorus that will be dissolved in single solvent earlier is heated to reflux temperature, adds the metaborate monohydrate rhodium chloride in the solution of thermotropism with this understanding then; Continue the reaction certain hour and obtain product [J.Am.Chem.Soc.1985; 107:2380-2388] [Org.Lett., 2010,12 (23): 5370-5373].Wherein, two kinds of reaction raw materials solubility of single solvent are relatively poor, and reaction system is mixed inhomogeneous, and reaction simultaneously is heated to reflux temperature earlier, makes reacting initial temperature higher, is easy to generate side reaction, and the two causes the product productive rate on the low side; In addition, under the condition of heating, add the solid rhodium chloride, not easy to operate, limited the popularization of reaction.
In order to address these problems, the present invention adopts method to be: at first add metaborate monohydrate rhodium chloride and triphenyl phosphorus, under the room temperature protection of nitrogen gas, add mixed solvent then, stir, heating up subsequently refluxes system again, continues reaction and obtains product.Wherein, earlier with metaborate monohydrate rhodium chloride and triphenyl phosphorus adding reaction unit, the low temperature safety simple to operate of feeding in raw material; Add mixed solvent, stirring at room is even, and gives reaction system the suitable reaction initiation time, heats up gradually more afterwards, makes the initiation reaction phase temperature hang down reaction raw materials is fully dissolved that therefore be difficult for the generation side reaction, the product productive rate is improved.
To sum up, the product productive rate that synthetic method of the present invention makes is high, and is simple to operate greater than 90%, process route safety, and reaction condition is gentle, and the three wastes are few, have bigger promotional value and economic results in society.
Summary of the invention:
One object of the present invention is to provide a kind of new method of synthetic Wilkinson type rhodium catalyst, and the technical scheme of employing is following:
Its reaction equation:
The first step: the rhodium trichloride hydrate of 1 molar equivalent and the triphenyl phosphorus of 3～6 molar equivalents are added in the there-necked flask, and the room temperature nitrogen protection adds mixed solvent down, and magnetic agitation is even, temperature rising reflux.
Second step: reaction system is rare red muddy from beginning, gradually becomes orange-yellow muddiness, has Maroon lake to generate then, stops reaction.
The 3rd step: nitrogen protection is filtered under the room temperature, uses the absolute ether cyclic washing, filters, and vacuum drying gets Wilkinson type rhodium catalyst.
Wherein, described rhodium trichloride hydrate of the first step and triphenyl phosphorus will at room temperature add;
The described mixed solvent of the first step is an absolute ethyl alcohol, absolute methanol, glycerine, a kind of and toluene in the ethylene glycol ethyl ether;
Want earlier before the described temperature rising reflux of the first step stirring under the system room temperature;
The said reflux temperature of the first step is 50～100 ℃
After second step, described aubergine deposition occurred, can continue to react 2h-8h;
First to the three said operation of step all will be carried out under nitrogen atmosphere.
The specific embodiment
To help to understand the present invention through following instance; But content of the present invention is not limited to the embodiment that lifts: (nuclear-magnetism is an AVANCE III 400MHz total digitalization nuclear magnetic resonance spectrometer; Test used medicine and be the pure or chemical pure of commercially available analysis, before the unexplained reference medicine uses all without purification process)
Embodiment 1
Get 0.15g rhodium trichloride hydrate, 0.8g triphenyl phosphorus in the 100mL there-necked flask, the room temperature nitrogen protection adds the mixed solution of 10mL absolute ethyl alcohol and 10mL toluene down, and magnetic agitation is even, is warming up to 80 ℃ of condensing refluxes gradually.Reaction begins the muddy system of rare redness for rhodium trichloride hydrate, and along with the carrying out of reaction, the system color shoals, and gradually becomes orange-yellow muddiness, begins to have the aubergine deposition to generate behind the 2h, stops reaction when continuing to be stirred to 5h.Be cooled to room temperature, nitrogen protection is filtered down, with 10mL absolute ether cyclic washing three times, filter, vacuum drying, aubergine powder (productive rate 96%).
1H?NMR：(400MHz，DMSO)：δ8.01-6.83(m，45H).
Embodiment 2
Get 0.15g rhodium trichloride hydrate, 0.8g triphenyl phosphorus in the 100mL there-necked flask, the room temperature nitrogen protection adds the mixed solution of 10mL absolute ethyl alcohol and 10mL toluene down, and magnetic agitation is even, is warming up to 60 ℃ of condensing refluxes gradually.Reaction begins the muddy system of rare redness for rhodium trichloride hydrate, and along with the carrying out of reaction, the system color shoals, and gradually becomes orange-yellow muddiness, begins to have the aubergine deposition to generate behind the 2h, stops reaction when continuing to be stirred to 5h.Be cooled to room temperature, nitrogen protection is filtered down, with 10mL absolute ether cyclic washing three times, filter, vacuum drying, aubergine powder (productive rate 90%).
1H?NMR：(400MHz，DMSO)：δ8.01-6.83(m，45H).
Embodiment 3
Get 0.15g rhodium trichloride hydrate, 0.5g triphenyl phosphorus in the 100mL there-necked flask, the room temperature nitrogen protection adds the mixed solution of 10mL absolute ethyl alcohol and 10mL toluene down, and magnetic agitation is even, is warming up to 80 ℃ of condensing refluxes gradually.Reaction begins the muddy system of rare redness for rhodium trichloride hydrate, and along with the carrying out of reaction, the system color shoals, and gradually becomes orange-yellow muddiness, begins to have the aubergine deposition to generate behind the 2h, stops reaction when continuing to be stirred to 5h.Be cooled to room temperature, nitrogen protection is filtered down, with 10mL absolute ether cyclic washing three times, filter, vacuum drying, aubergine powder (productive rate 91%).
1H?NMR：(400MHz，DMSO)：δ8.01-6.83(m，45H).
Embodiment 4
Get 0.15g rhodium trichloride hydrate, 0.8g triphenyl phosphorus in the 100mL there-necked flask, the room temperature nitrogen protection adds the mixed solution of 10mL ethylene glycol ethyl ether and 10mL toluene down, and magnetic agitation is even, is warming up to 80 ℃ of condensing refluxes gradually.Reaction begins the muddy system of rare redness for rhodium trichloride hydrate, and along with the carrying out of reaction, the system color shoals, and gradually becomes orange-yellow muddiness, begins to have the aubergine deposition to generate behind the 2h, stops reaction when continuing to be stirred to 5h.Be cooled to room temperature, nitrogen protection is filtered down, with 10mL absolute ether cyclic washing three times, filter, vacuum drying, aubergine powder (productive rate 93%).
1H?NMR：(400MHz，DMSO)：δ8.01-6.83(m，45H).
Embodiment 5
Get 0.15g rhodium trichloride hydrate, 0.8g triphenyl phosphorus in the 100mL there-necked flask, the room temperature nitrogen protection adds the mixed solution of 10mL ethylene glycol ethyl ether and 10mL toluene down, and magnetic agitation is even, is warming up to 100 ℃ of condensing refluxes gradually.Reaction begins the muddy system of rare redness for rhodium trichloride hydrate, and along with the carrying out of reaction, the system color shoals, and gradually becomes orange-yellow muddiness, begins to have the aubergine deposition to generate behind the 2h, stops reaction when continuing to be stirred to 5h.Be cooled to room temperature, nitrogen protection is filtered down, with 10mL absolute ether cyclic washing three times, filter, vacuum drying, aubergine powder (productive rate 92%).
1H?NMR：(400MHz，DMSO)：δ8.01-6.83(m，45H).
Embodiment 6
Get 5mg Wilkinson type rhodium catalyst-RhCl (PPh
3)
3, 5mg cuprous iodide, 34mg 2-(o-methyl-benzene) yl pyridines, 50mg benzoic acid in the 100mL there-necked flask, the room temperature nitrogen protection adds 10mLN-methyl pyrrolidone (NMP) solution down, magnetic agitation is even; Be warming up to 130 ℃ of reaction 36h, stop reaction, be cooled to room temperature; Add 10mL ethyl acetate, filter, (eluant, eluent is an ethyl acetate to filtrating: benzinum=5: 1) through column chromatography for separation; Obtain ortho position aryl acyloxylation product (productive rate: 68%), reaction equation is following:
1H?NMR(CDCl
3，400MHz)：δ8.65-8.63(m，1H)，7.86-7.83(m，2H)，7.64-7.49(m，2H)，7.38-7.13(m，7H)，2.19(s，3H)。
Claims (9)
1. the new method of a synthetic Wilkinson type rhodium catalyst is characterized in that, the technical scheme of employing is following:
The first step: rhodium trichloride hydrate and triphenyl phosphorus are added in the there-necked flask, and the room temperature nitrogen protection adds mixed solvent down, and magnetic agitation is even, temperature rising reflux;
Second step: reaction system is rare red muddy from beginning, gradually becomes orange-yellow muddiness, has the aubergine deposition to generate then, stops reaction;
The 3rd step: nitrogen protection is filtered under the room temperature, uses the absolute ether cyclic washing, filters, and is dry under the vacuum, gets the Wilkinson rhodium catalyst.
2. synthetic method as claimed in claim 1 is characterized in that the rhodium trichloride hydrate described in the first step reaction and the mol ratio of phosphine part are: 1: 3～6.
3. synthetic method as claimed in claim 1 is characterized in that adding rhodium trichloride hydrate and triphenyl phosphorus under the room temperature in the first step reaction.
4. synthetic method as claimed in claim 1 is characterized in that the mixed solvent described in the first step reaction is an absolute ethyl alcohol, absolute methanol, glycerine, a kind of and toluene in the ethylene glycol ethyl ether.
5. synthetic method as claimed in claim 1 is characterized in that adding mixed solvent under the room temperature in the first step reaction.
6. synthetic method as claimed in claim 1, the back that it is characterized in that stirring under the room temperature in the first step reaction is at temperature rising reflux gradually.
7. synthetic method as claimed in claim 1, it is characterized in that purplish red or dark pink colour deposition occurs in the second step reaction after, can continue to react 2h-8h.
8. synthetic method as claimed in claim 1 is characterized in that said operation all will carry out under nitrogen atmosphere.
9. synthetic method as claimed in claim 1 is characterized in that described reaction can carry out under 50～100 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108125953A (en) * | 2017-12-27 | 2018-06-08 | 湖北工业大学 | Aromatic ester compound is used to prepare anti-ADV-7 viral agents |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0805138B1 (en) * | 1996-04-30 | 2001-03-28 | Celanese Chemicals Europe GmbH | Process for the hydroformylation of olefinic unsaturated compounds |
| CN101353359A (en) * | 2008-09-19 | 2009-01-28 | 浙江省冶金研究院有限公司 | Microwave synthetic method of tri(triphenylphosphine) rhodium chloride |
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- 2012-04-13 CN CN2012101073918A patent/CN102658204A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0805138B1 (en) * | 1996-04-30 | 2001-03-28 | Celanese Chemicals Europe GmbH | Process for the hydroformylation of olefinic unsaturated compounds |
| CN101353359A (en) * | 2008-09-19 | 2009-01-28 | 浙江省冶金研究院有限公司 | Microwave synthetic method of tri(triphenylphosphine) rhodium chloride |
Non-Patent Citations (1)
| Title |
|---|
| 潘丽娟等: "三苯基膦氯化铑的合成研究", 《稀有金属材料与工程》, vol. 37, 31 October 2008 (2008-10-31), pages 681 - 683 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108125953A (en) * | 2017-12-27 | 2018-06-08 | 湖北工业大学 | Aromatic ester compound is used to prepare anti-ADV-7 viral agents |
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Application publication date: 20120912 |