CN102372745A - Preparation method of hydroformylation catalyst precursor - Google Patents
Preparation method of hydroformylation catalyst precursor Download PDFInfo
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- CN102372745A CN102372745A CN2010102647446A CN201010264744A CN102372745A CN 102372745 A CN102372745 A CN 102372745A CN 2010102647446 A CN2010102647446 A CN 2010102647446A CN 201010264744 A CN201010264744 A CN 201010264744A CN 102372745 A CN102372745 A CN 102372745A
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- triphenylphosphine
- rhodium
- alkane
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- acetylacetone
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Abstract
The invention discloses a method for synthesizing acetylacetone triphenylphosphine carbonyl rhodium, comprising the following steps of: respectively adding acetylacetone dicarbonyl rhodium and triphenylphosphine into alkane, mixing the acetylacetone dicarbonyl rhodium and triphenylphosphine, heating to cause mixture to be maintained to be in a backflow state for 10-30 mintues, stopping heating, cooling to room temperature, filtering and drying to obtain the product acetylacetone triphenylphosphine carbonyl rhodium. By adopting the technical scheme provided by the invention, the acetylacetone triphenylphosphine carbonyl rhodium can be prepared with acetylacetone triphenylphosphine dicarbonyl rhodium in the air, and the defect that the condition of insert gas protection is required in the prior art can be overcome, thus a preparation process is simplified and efficiency is improved.
Description
Technical field
The present invention relates to a kind of compound method of precious metal organic cpds.Specifically, relate to a kind of method of claiming methyl ethyl diketone triphenylphosphine rhodium carbonyl of closing.
Background technology
A kind of catalyst precursor that hydroformylation of olefin is commonly used is a methyl ethyl diketone triphenylphosphine rhodium carbonyl.This compound is stable in the air, is easy to preserve.With being converted into the catalyst activity structure rapidly in its adding hydroformylation reaction system, bring into play katalysis then expeditiously.This catalyst precursor of a large amount of uses in the industrial installation of hydroformylation of olefin.
The synthetic of methyl ethyl diketone triphenylphosphine rhodium carbonyl is shown in J.Chem.Soc., 3156 (1964) the earliest.This method uses rhodium dicarbonyl acetylacetonate to be raw material.At first it is dissolved in and forms solution in the benzene, in solution, drip the benzole soln of triphenylphosphine afterwards, reaction takes place immediately, emits CO gas.Finish the back and extract benzene, resistates washs with ether, separates obtaining product again through post.Because all very easily oxidations of benzole soln of raw material and product.Therefore above-mentioned steps need be carried out under protection of inert gas.This reaction almost can be carried out quantitatively, and yield is very high.
On the 43rd page of " precious metal " magazine 2005 the 26th volume first phase, put down in writing a similar method, changed benzene solvent into toluene solvant in the method, but still need under nitrogen protection, react.The document does not provide the yield of reaction separately.
The preparation method who also has some to adopt other raw materials for example adopts methyl ethyl diketone two (triphenylphosphine) to change rhodium etc.The synthesis step of these methods is more, and total recovery is lower.
Summary of the invention
The technical problem that the present invention will solve is:
In the prior art, the reaction needed that is prepared methyl ethyl diketone triphenylphosphine rhodium carbonyl by rhodium dicarbonyl acetylacetonate is carried out under protection of inert gas, makes troubles for preparation process preparation process especially in enormous quantities.The objective of the invention is to change the reaction solvent for use, the preparation process can be carried out in air, so simplify the operation, raise the efficiency.
Have now found that it is stable that the alkane solution of rhodium dicarbonyl acetylacetonate can keep in air.And the solubleness of product methyl ethyl diketone triphenylphosphine rhodium carbonyl in alkane is very low, in case formation just can be separated out from solution immediately and kept stable.
Technical scheme of the present invention is:
(1) in rhodium dicarbonyl acetylacetonate, adds suitable alkane and be heated to backflow.Used alkane solvent can be the straight or branched alkane of C5-C12 scope, can be pure compound, also can be mixture, for example normal hexane, Skellysolve A, normal heptane, sherwood oil, industrial hexane etc.
(2) in triphenylphosphine, add alkane and heating, triphenylphosphine is all dissolved.Used alkane can with (1) in identical, also can be different.The amount that adds triphenylphosphine presses 0.95 with (1) middle amount that adds rhodium dicarbonyl acetylacetonate: 1-1.2: 1, preferred 1: 1-1.1: the proportioning of 1 (mol ratio).
(3) above-mentioned triphenylphosphine drips of solution is added in the rhodium dicarbonyl acetylacetonate solution, heating simultaneously makes mixture keep reflux state 10-30 minute.
(4) stop heating, reduce to room temperature, filter also and obtain product methyl ethyl diketone triphenylphosphine rhodium carbonyl after the drying.
The invention has the beneficial effects as follows:
The technical scheme that adopts the present invention to propose prepares methyl ethyl diketone triphenylphosphine rhodium carbonyl by methyl ethyl diketone phenylbenzene rhodium can carry out in air, needing in the prior art to have avoided the condition of protection of inert gas, and the preparation process is simplified, and has improved efficient.
Embodiment
Embodiment 1
The 350ml normal hexane is added in the 17.0g rhodium dicarbonyl acetylacetonate, be heated to backflow under stirring, let rhodium dicarbonyl acetylacetonate all dissolve.In addition the 50ml normal hexane is added in the 18.1g triphenylphosphine, be heated to backflow under stirring, let triphenylphosphine all dissolve.The hexane solution of triphenylphosphine is added drop-wise in the hexane solution of rhodium dicarbonyl acetylacetonate, produces gas immediately and faint yellow crystallization production is arranged, be added dropwise to complete the back and under refluxing, continue reaction 15 minutes; Stop heating; Cooling is filtered, and is dry under vacuum; Obtain methyl ethyl diketone triphenylphosphine rhodium carbonyl product, filtrating can recycle.This method is 99.8% in the product yield of rhodium.
Embodiment 2
According to embodiment 1, just change solvent into Skellysolve A, obtain product at last.Product yield in rhodium is 99.6%.
Embodiment 3
According to embodiment 1, just change solvent into sherwood oil, obtain product at last.Product yield in rhodium is 99.6%.
Embodiment 4
According to embodiment 1, just change solvent into normal heptane, obtain product at last.Product yield in rhodium is 99.7%.
Embodiment 5
According to embodiment 1, just change solvent into industrial hexane, obtain product at last.Product yield in rhodium is 99.7%.
Claims (6)
1. the method for a synthesis of acetyl acetone triphenylphosphine rhodium carbonyl comprises the steps:
(1) in rhodium dicarbonyl acetylacetonate, adds alkane and be heated to backflow
(2) in triphenylphosphine, add alkane and heating, triphenylphosphine is all dissolved, the amount that adds rhodium dicarbonyl acetylacetonate in the amount of adding triphenylphosphine and (1) is by 0.95: 1-1.2: the proportioning of 1 (mol ratio)
(3) above-mentioned triphenylphosphine drips of solution is added in the rhodium dicarbonyl acetylacetonate solution, heating simultaneously makes mixture keep reflux state 10-30 minute
(4) stop heating, reduce to room temperature, filter also and obtain product methyl ethyl diketone triphenylphosphine rhodium carbonyl after the drying.
2. method according to claim 1, wherein alkane is the pure compound or the mixture of the straight or branched alkane of C5-C12 scope.
3. method according to claim 1 and 2, wherein alkane is normal hexane, Skellysolve A, normal heptane, sherwood oil or industrial hexane.
4. method according to claim 1, the amount of the rhodium dicarbonyl acetylacetonate that adds in the amount of the triphenylphosphine that wherein adds in the step (2) and the step (1) is by 1: 1-1.1: the proportioning of 1 (mol ratio).
5. method according to claim 1, wherein step (1) is with a kind of material with the middle alkane that adds of step (2).
6. method according to claim 5, wherein alkane is normal hexane, Skellysolve A, normal heptane, sherwood oil or industrial hexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2010102647446A CN102372745A (en) | 2010-08-27 | 2010-08-27 | Preparation method of hydroformylation catalyst precursor |
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| CN2010102647446A CN102372745A (en) | 2010-08-27 | 2010-08-27 | Preparation method of hydroformylation catalyst precursor |
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| CN2010102647446A Pending CN102372745A (en) | 2010-08-27 | 2010-08-27 | Preparation method of hydroformylation catalyst precursor |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702270A (en) * | 2012-05-25 | 2012-10-03 | 杭州凯大催化金属材料有限公司 | Solvent-free synthesis method of acetylacetonatocarbonyltriphenylphosphine |
| JP2015520134A (en) * | 2012-04-25 | 2015-07-16 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフトＵｍｉｃｏｒｅ ＡＧ ＆ Ｃｏ．ＫＧ | Process for preparing diketonato-rhodium (I) -carbonyl complexes |
| CN111978353A (en) * | 2020-07-30 | 2020-11-24 | 西安凯立新材料股份有限公司 | Preparation method of rhodium complex |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4409149A (en) * | 1981-06-29 | 1983-10-11 | Union Carbide Corporation | Process for producing catalyst precursors |
-
2010
- 2010-08-27 CN CN2010102647446A patent/CN102372745A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4409149A (en) * | 1981-06-29 | 1983-10-11 | Union Carbide Corporation | Process for producing catalyst precursors |
Non-Patent Citations (2)
| Title |
|---|
| A. M. TRZECIAK等,: "Structure, Electrochemistry and Hydroformylation Catalytic Activity of the Bis(pyrazolylborato)rhodium(I) Complexes [RhBp(CO)P] [P = P(NC4H4)3, PPh3, PCy3, P(C6H4OMe-4)3]", 《EUR. J. INORG. CHEM.》, vol. 2004, no. 7, 17 February 2004 (2004-02-17) * |
| TIC WILHELM J.等,: "The synthesis of a rhodium catalyst for hydroformylation of propylene", 《PRZEMYSL CHEMICZNY》, vol. 81, no. 6, 30 June 2002 (2002-06-30) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015520134A (en) * | 2012-04-25 | 2015-07-16 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフトＵｍｉｃｏｒｅ ＡＧ ＆ Ｃｏ．ＫＧ | Process for preparing diketonato-rhodium (I) -carbonyl complexes |
| CN102702270A (en) * | 2012-05-25 | 2012-10-03 | 杭州凯大催化金属材料有限公司 | Solvent-free synthesis method of acetylacetonatocarbonyltriphenylphosphine |
| CN111978353A (en) * | 2020-07-30 | 2020-11-24 | 西安凯立新材料股份有限公司 | Preparation method of rhodium complex |
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Application publication date: 20120314 |