CN101723984B - Method for preparing carbonyltris(triphenylphosphine)rhodium(I) hydride in batch - Google Patents
Method for preparing carbonyltris(triphenylphosphine)rhodium(I) hydride in batch Download PDFInfo
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- CN101723984B CN101723984B CN200810225600A CN200810225600A CN101723984B CN 101723984 B CN101723984 B CN 101723984B CN 200810225600 A CN200810225600 A CN 200810225600A CN 200810225600 A CN200810225600 A CN 200810225600A CN 101723984 B CN101723984 B CN 101723984B
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- trichloride hydrate
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Abstract
The invention relates to a method for preparing carbonyltris(triphenylphosphine)rhodium(I) hydride in batch, which takes hydrated rhodium chloride as raw material to prepare thecarbonyltris(triphenylphosphine)rhodium(I) hydride, overcomes the defects of excessive usage quantity of reactive solvent and low yield of metal rhodium in the prior art. The invention aims at further improving method of synthesis, optimizing conditions for synthesis, and increasing the yield of products. In the invention, the reactive solvent is changed from alcohol to anhydrous alcohol, and the solvent usage quantityper unit of reactive material is reduced by 5 to 10 times. The size of a reactor is greatly reduced correspondingly, thereby facilitating the batch synthesis of complex compound, and greatly reducingeffects on the environment. The method increases the yield of the metal rhodium from about 94 percent in prior art to 98 percent, greatly increases the utilization ratio of precious metals, and brings economic benefits because the metal rhodium is quite expensive.
Description
Technical field
The present invention relates to the compound method of precious metal organic complex, particularly a kind of method that is used for three (triphenylphosphine) carbonyl hydrogen rhodium batch preparations.
Prior art
Three (triphenylphosphine) carbonyl hydrogen rhodium is a kind of precious metal organic complex.The catalyzer that often is used as the alkene carbongl group synthesis reaction.Because the natural resources of metal rhodium is rare, its price is very expensive, and the compound method of relevant rhodium compound comes into one's own always, and the step that wherein simplifies the operation is the major objective of pursuing with the yield that improves metal rhodium.
Three (triphenylphosphine) carbonyl hydrogen rhodium has several kinds of different compound methods.Be recorded in J.Am.Chem.Soc.85,3500, the method in (1963) is the method that proposes the earliest.With trans-two (triphenylphosphine) carbonyl chlorine rhodium is raw material, is reductive agent with the hydrazine, obtains product through reactions:
RhCL(CO)[P(C
6H
5)
3]
2+P(C
6H
5)
3+H
2N-NH
2→
HRh(CO)[P(C
6H
5)
3]
3+H
2N-NHCL
In J.Chem.Soc. (A) 1968,2660, having put down in writing improving one's methods of a kind of aforesaid method, is raw material with trans-two (triphenylphosphine) carbonyl chlorine rhodium equally, and using Peng Qinghuana instead is reductive agent, and product yield is 90%.It is that raw material is processed trans-two (triphenylphosphine) carbonyl chlorine rhodium midbody earlier that the document has been put down in writing with the rhodium trichloride hydrate simultaneously:
RhCL
3·nH
2O+2P(C
6H
5)
3+HCHO→RhCL(CO)[P(C
6H
5)
3]
2
Make use of momentum afterwards and add that Peng Qinghuana continues reaction and so-called " step " synthesis method of obtaining product.Because rhodium trichloride hydrate is the most frequently used initial feed of preparation rhodium-organic complex, therefore " step " method is obviously simpler.The total recovery of record counts 72% with rhodium trichloride hydrate.
USP 3,644 proposes to use the similar approach of KOH-ethanolic soln as reductive agent in 446.But need in the reaction to feed CO and H2 gas earlier, do not report the reaction yield situation.
Put down in writing use KOH-ethanolic soln among the J.C.S.Dalton 1972,843 as reductive agent but need not to feed improving one's methods of CO and H2, the yield 94% of product.
Through people's effort, three (triphenylphosphines) but still exist some shortcoming and defect though the compound method of carbonyl hydrogen rhodium is improved.Such as, aspect the use of reaction solvent, the usage quantity of etoh solvent is very big in the prior art, and the ethanol volumeter (milliliter/gram) so that the unit mass rhodium trichloride hydrate need add generally reaches 200 times, is up to 500 times.Like this; If the batch that adopts prior art to carry out three (triphenylphosphine) carbonyl hydrogen rhodium synthesizes; The reaction volume of production unit quality product will be very big, directly causes huge, preparation process complicated and uneconomical of conversion unit, also environment affected greatly simultaneously.For another example, the yield of product is high not enough in the prior art, because the price of metal rhodium is extremely expensive.Generally, the every raising 1% of yield just can bring very big economic benefit.Prior art also exists many aspects that are further improved, and is all the more so during especially as batch synthesis method.
Summary of the invention
Consumption to reaction solvent in the prior art is excessive, the shortcoming that the metal rhodium yield is not high.The objective of the invention is further to improve compound method, especially optimize synthesis condition, improve the yield of product, be suitable for the preparation method of in batches synthetic three (triphenylphosphine) carbonyl hydrogen rhodium in the hope of formation.
The contriver finds, is that raw material carries out in the building-up process of three (triphenylphosphine) carbonyl hydrogen rhodium with the rhodium trichloride hydrate, and the use of reaction solvent is very important.On the one hand, to the first step reaction, i.e. the reaction of the synthetic triphenylphosphine rhodium chloride midbody of rhodium trichloride hydrate and triphenylphosphine, the water-content in the reaction solvent has very big influence to reaction result, when water cut is too much, can cause product yield to reduce.On the other hand, with regard to entire reaction, the use total amount of reaction solvent can reduce greatly; This not only can not cause the minimizing of yield; Because of reducing back dissolved product amount with filtrate discharge, the total solvent amount reduces simultaneously on the contrary, thus the yield of raising product, the solution loss of minimizing rhodium metal.
The batch preparation of the present invention's a kind of three (triphenylphosphine) carbonyl hydrogen rhodium is feedstock production three (triphenylphosphine) carbonyl hydrogen rhodium with the rhodium trichloride hydrate, and reaction solvent changes absolute ethyl alcohol into by ethanol, and reduces the usage quantity of solvent.
The present invention is a kind of to be the method for feedstock production three (triphenylphosphine) carbonyl hydrogen rhodium with the rhodium trichloride hydrate, comprises the steps:
A) rhodium trichloride hydrate is dissolved in the absolute ethyl alcohol, more above-mentioned solution is splashed into and stir down and be in the triphenylphosphine-ethanol solution of reflux state, fully obtain the ethanolic soln of midbody three (triphenylphosphine) rhodium chloride after the reaction; Wherein the concentration of rhodium trichloride hydrate-ethanolic soln is 4%-12%; The concentration of triphenylphosphine-ethanolic soln is 25%-50%, and the mass ratio of rhodium trichloride hydrate and triphenylphosphine is 1: 8-1: 10.
B) join by in the reaction mixture that a) obtains formalin is disposable; Fully obtain the ethanolic soln of second kind of midbody trans-two (triphenylphosphine) carbonyl chlorine rhodium after the reaction; Wherein the concentration of formalin is 37%-40%, and the mass ratio of rhodium trichloride hydrate add-on is 1: 16-1 in its add-on and the preceding step: 26.
(C)) c) join by b KOH-ethanolic soln is disposable) in the reaction mixture that obtains,, obtain final reaction product in reflux temperature fully reaction down; Wherein the concentration of KOH-ethanolic soln is 20%-26.5%, KOH and a) in add rhodium trichloride hydrate mass ratio be 1: 4.5-1: 5.5.
D) will filter by (c) resultant product, wash, conventional processing such as drying obtains the finished product three (triphenylphosphine) carbonyl hydrogen rhodium.
Beneficial effect of the present invention:
Proposing technical scheme according to the present invention, with the rhodium trichloride hydrate to be that raw material carries out the batch of three (triphenylphosphine) carbonyl hydrogen rhodium synthetic, and compared with prior art, the solvent usage quantity of unit reaction raw materials has reduced by 5-10 times.Make thus that the volume of reactor drum is corresponding to be reduced greatly, more convenient and easy when making synthetic this in batches complex compound.Owing to reduced the usage quantity of organic solvent, also significantly reduced influence to environment.
Technical scheme of the present invention makes the yield of Noble Metal Rhodium bring up to the rate of utilization that 98% one side improves the precious metal resource greatly by of the prior art about 94%.Because the metal rhodium price is very expensive, can bring considerable economic benefit thus on the other hand.
Embodiment:
Embodiment 1
The ethanol solution 75ml that is dissolved with the 2.618g rhodium trichloride hydrate is added drop-wise among the ethanol solution 100ml that is dissolved with the 26.43g triphenylphosphine under the reflux state, and system has a large amount of garnet crystallizations to generate.Continued reflux 1 hour.Under the fierce agitation condition, in above-mentioned reaction mixture, add formaldehyde solution 60ml, change yellow fully into by garnet until the reaction mixture color.Add fast the ethanol solution 50ml that is dissolved with 14.0g Pottasium Hydroxide, reflux 10 hours generates to the glassy yellow mixture.Aftertreatment: at first, with the reaction mixture heat filtering; Then, use absolute ethyl alcohol, deionized water, absolute ethanol washing filter cake successively; At last, product is carried out decompress filter, to complete drying.Getting product is the glassy yellow crystallization, and 8.71g collects rate 98.8% with rhodium.
Embodiment 2
The 95% ethanolic soln 75ml that is dissolved with the 7.80g rhodium trichloride hydrate is joined among the 95% ethanolic soln 100ml that is dissolved with the 62.70g triphenylphosphine under the reflux state, and system has a large amount of garnet crystallizations to generate.Continued reflux 1 hour.Under the fierce agitation condition, in above-mentioned reaction mixture, add formaldehyde solution 120ml, change yellow fully into by garnet until the reaction mixture color.Add fast the freshly prepared ethanol solution 150ml that is dissolved with 42.2g Pottasium Hydroxide, reflux 12 hours generates to the glassy yellow mixture.Aftertreatment: at first, with the reaction mixture heat filtering; Then, use absolute ethyl alcohol, deionized water, absolute ethanol washing filter cake successively; At last, product is carried out decompress filter, to complete drying.Getting product is the glassy yellow crystallization, and 23.84g collects rate 89.8% with rhodium.The result shows that the yield that reacts when using aqueous ethanol obviously reduces.
Embodiment 3
The ethanol solution 750ml that is dissolved with the 78.25g rhodium trichloride hydrate is joined among the ethanol solution 1000ml that is dissolved with the 629.00g triphenylphosphine under the reflux state, and system has a large amount of garnet crystallizations to generate.Continued reflux 1 hour.Under the fierce agitation condition, in above-mentioned reaction mixture, add formaldehyde solution 1200ml, change yellow fully into by garnet until the reaction mixture color.Add fast the freshly prepared ethanol solution 1500ml that is dissolved with 420.0g Pottasium Hydroxide, reflux 12 hours generates to the glassy yellow mixture.Aftertreatment: at first, with the reaction mixture heat filtering; Then, use absolute ethyl alcohol, deionized water, absolute ethanol washing filter cake successively; At last, product is carried out decompress filter, to complete drying.Getting product is the glassy yellow crystallization, and 261.14g collects rate 98.0% with rhodium.
Claims (1)
1. the batch preparation of (triphenylphosphine) carbonyl hydrogen rhodium is feedstock production three (triphenylphosphine) carbonyl hydrogen rhodium with the rhodium trichloride hydrate, it is characterized in that reaction solvent is an absolute ethyl alcohol, reduces the usage quantity of solvent, comprises the steps:
A) rhodium trichloride hydrate is dissolved in the absolute ethyl alcohol; Again above-mentioned solution is splashed into and stir down and be in the triphenylphosphine-ethanol solution of reflux state, fully obtain the ethanolic soln of midbody three (triphenylphosphine) rhodium chloride after the reaction; The concentration of wherein said rhodium trichloride hydrate-ethanolic soln is 4%-12%; The concentration of triphenylphosphine-ethanolic soln is 25%-50%, and the mass ratio of rhodium trichloride hydrate and triphenylphosphine is 1: 8-1: 10;
B) join by in the reaction mixture that a) obtains formalin is disposable; Fully obtain the ethanolic soln of second kind of midbody trans-two (triphenylphosphine) carbonyl chlorine rhodium after the reaction; Wherein the concentration of formalin is 37%-40%, and the mass ratio of rhodium trichloride hydrate add-on is 1 in its add-on and the preceding step: 16-1: 26;
(c) join by b the KOH-ethanolic soln is disposable) in the reaction mixture that obtains,, obtain final reaction product in reflux temperature fully reaction down; Wherein the concentration of KOH-ethanolic soln is 20%-26.5%, KOH and a) in add rhodium trichloride hydrate mass ratio be 1: 4.5-1: 5.5;
D) will filter by (c) resultant product, wash, dry conventional processing obtains the finished product three (triphenylphosphine) carbonyl hydrogen rhodium.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102503985B (en) * | 2011-10-25 | 2014-12-17 | 中国海洋石油总公司 | Preparation method for hydridocarbonyltris-(tri-phenylphosphine)-rhodium |
| CN102408451A (en) * | 2011-10-25 | 2012-04-11 | 中国海洋石油总公司 | Preparation method of trans-carbonylchlorobis(triphenylphosphine)rhodium |
| CN102391312B (en) * | 2011-10-25 | 2014-09-17 | 中国海洋石油总公司 | Preparation method for palladium-tetrakis(triphenylphosphine) rhodium hydroxide |
| JP6661556B2 (en) * | 2014-07-11 | 2020-03-11 | 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 | Preparation process of hydridecarbonyltris (triphenylphosphine) rhodium (I) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644446A (en) * | 1969-07-01 | 1972-02-22 | Union Oil Co | Preparation of rhodium and iridium hydride carbonyl complexes |
| CN101172897A (en) * | 2007-10-31 | 2008-05-07 | 福建省农业科学院农业工程技术研究所 | Plastic tents type heap ferment method and device for fertilizer |
| CN101357341A (en) * | 2007-07-31 | 2009-02-04 | 顾鸣海 | Hydrogenation technique rhodium catalyst for producing antibiotic doxycycline and use thereof |
-
2008
- 2008-10-30 CN CN200810225600A patent/CN101723984B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644446A (en) * | 1969-07-01 | 1972-02-22 | Union Oil Co | Preparation of rhodium and iridium hydride carbonyl complexes |
| CN101357341A (en) * | 2007-07-31 | 2009-02-04 | 顾鸣海 | Hydrogenation technique rhodium catalyst for producing antibiotic doxycycline and use thereof |
| CN101172897A (en) * | 2007-10-31 | 2008-05-07 | 福建省农业科学院农业工程技术研究所 | Plastic tents type heap ferment method and device for fertilizer |
Non-Patent Citations (1)
| Title |
|---|
| S. S. Bath, et al.."Five-Coordinate Hydrido-Carbonyl Complexes of Rhodium and Iridium and their Analogy with COH(CO".《J. Am. Chem. Soc.》.1963,第85卷(第21期),第3500-3501页. |
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