CN1046533C - Process for preparing rhodium 3[3 (meta-sulfonate phenyl) phosphine] -carbonyl hydride - Google Patents
Process for preparing rhodium 3[3 (meta-sulfonate phenyl) phosphine] -carbonyl hydride Download PDFInfo
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- CN1046533C CN1046533C CN 96120649 CN96120649A CN1046533C CN 1046533 C CN1046533 C CN 1046533C CN 96120649 CN96120649 CN 96120649 CN 96120649 A CN96120649 A CN 96120649A CN 1046533 C CN1046533 C CN 1046533C
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- phosphine
- phenyl
- rhodium
- sulfonate phenyl
- sulfonate
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Abstract
The present invention relates to a method for preparing 3[3 (meta-sulfonate phenyl) phosphine]-carbonyl rhodium hydride, which comprises that CO is led into the alcohol solution of a rhodium compound for reacting for 10 to 60 minutes at the reaction temperature of 60 to 100 DEG C, a 3 (meta-sulfonate phenyl) phosphine water solution having the molar ratio of 3.0 to 6.0 with rhodium is dropped, the pH value of reaction liquid is regulated by 8 to 14, the gas mixture of hydrogen gas and the CO having the molar ratio of 0.1 to 5.0 is led in for reacting for 2 to 6 hours, and then, recovered products are separated. The method has the advantages of short reaction time and high product yield.
Description
The invention relates to the preparation method of the organic compound that contains periodic table of elements VIII family element, the preparation method of [three (-sulfonate phenyl) phosphine] carbonyl hydrogenation Rh of more specifically saying so about three.
Three [three (-sulfonate phenyl) phosphines] carbonyl hydrogenation Rh has good catalytic activity to the reaction of alkene formylation system aldehyde in oil-water two-phase system.According to J.Organomet.chem.389,85～101,1990 disclosed preparation methods are with Rh
2(CH
3COO)
4, three (-sodium sulfonate phenyl) phosphine (being TPPTS) and CO and H
2Gas mixture in the methanol solution of sodium hydroxide in 70 ℃ of temperature of reaction, reaction is 12 hours under the condition of reaction pressure 70 crust, a carbonyl hydrogenation Rh Rh H (CO) (TPPTS) can to obtain three [three (a sodium sulfonate phenyl) phosphines]
3, with this preparation method prepare three [three (-sodium sulfonate phenyl) phosphine] though-that the yield of carbonyl hydrogenation Rh can reach 80 heavy % reaction pressures is too high, the reaction times is long, also discloses another preparation method in the document, is about to Rh (CO)
2(acac) and TPPTS in the aqueous solution with CO reaction 18 hours, can obtain RhH (CO) (TPPTS)
3Though this method does not need higher pressure, the reaction times is still longer, and product yield only has 70 heavy %, and the document has also been described with RhCl in addition
33H
2O is a raw material, and formaldehyde is made reductive agent, the preparation method who in the methanol solution of sodium hydroxide, reacts with TPPTS, but sepn process is comparatively complicated, does not report yield.
It is oversize to the objective of the invention is to overcome the prior art reaction times, and the shortcoming that yield is lower provides a kind of and can shorten the preparation method that the reaction times has three [three (-sulfonate phenyl) phosphines] carbonyl hydrogenation Rh of higher yields again.
Method provided by the invention is included in the alcoholic solution of the compound that under 60～100 ℃ the temperature of reaction carbon monoxide is fed rhodium reacted 10～60 minutes, drip and the mol ratio of rhodium is three (-sulfonate phenyl) phosphine aqueous solution of 3.0～6.0, conditioned reaction liquid pH value to 8～14, feed hydrogen and carbon monoxide mol ratio and be 0.1～5.0 the hydrogen and the gas mixture of carbon monoxide and reacted 2～6 hours, Separation and Recovery product three [three (-the sulfonate phenyl) phosphine] carbonyl hydrogenation Rh.
The compound of described rhodium is selected from one or more in the compound of soluble rhodium in alcohol, in the halogenide of preferred rhodium one or more, as the muriate of rhodium, the bromide of rhodium and the iodide of rhodium, the muriate of more preferred rhodium, as contain the Trichlororhodium of crystal water.
Described alcohol is selected from one or more in the alcohol that is in liquid state under described reaction conditions, comprise methyl alcohol, ethanol, propyl alcohol-1, propyl alcohol-2, propylene glycol, glycerol, butanols-1, butanols-2, butyleneglycol, trihydroxybutane, amylalcohol-1, amylalcohol-2, amyl alcohol-3, amylalcohol, hexanol, hexalin, phenylcarbinol, phenylethyl alcohol etc., wherein one or more in particular methanol, ethanol, propyl alcohol-1, propyl alcohol-2, butanols-1, the butanols 2 with two above hydroxyls.More particular methanol or ethanol or their mixture can contain 5 heavy % with interior water in the described alcoholic solution.
The concentration of described rhodium compound alcoholic solution or three (-sulfonate phenyl) the phosphine aqueous solution can change to the scope of its saturated solution at rarer solution, but employed quantity of solvent was too big when solution was too rare, can increase treatment capacity, thereby preferred 0.08 mol of the concentration of rhodium compound alcoholic solution is to its saturated solution, more preferred 0.08 mol～0.80 mol, preferred 0.18 mol of concentration of three (-sulfonate phenyl) phosphine aqueous solution is to its saturated solution, more preferred 0.18 mol～1.70 mol.
In described three (-sulfonate phenyl) phosphine preferred three (-sulfonic acid lithium phenyl) phosphine, three (-sodium sulfonate phenyl) phosphine, three (-potassium sulfonate phenyl) phosphine, three (-sulfonic acid rubidium phenyl) phosphine, three (-sulfonic acid caesium phenyl) phosphine, three (-ammonium sulphonate phenyl) phosphine one or more.In more preferred three (-sodium sulfonate phenyl) phosphine, three (-potassium sulfonate phenyl) phosphine, three (-ammonium sulphonate phenyl) phosphine one or more, preferably three (-sodium sulfonate phenyl) phosphine is TPPTS.
The mol ratio of described three (-sulfonate phenyl) phosphine and rhodium can change preferred 3.0～4.0 in 3.0～6.0 scope.
The pH value of described regulator solution can be selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, the ammonia one or more the aqueous solution, alcoholic solution or pure water mixed solution and regulates the aqueous solution of preferred sodium hydroxide, lithium hydroxide or ammonia with containing.
The mol ratio of hydrogen and carbon monoxide can be 0.1～5.0 in described hydrogen and the carbon mono oxide mixture, preferred 0.5～3.0.
The separation of described three [three (-sulfonate phenyl) phosphine] carbonyl hydrogenation Rh can be by J.Organomet.chem.389,99,1990 described methods are carried out, also can in reaction product, add alcohol excess, and be cooled to 10～25 ℃, [three (-sulfonate phenyl) phosphine] carbonyl hydrogenation Rh is separated out to make three, after filtration, washing, under vacuum in 40～80 ℃ of dryings, [three (-sulfonate phenyl) phosphine] carbonyl hydrogenation Rh that obtains three.
Method provided by the invention has short, yield advantage of higher of reaction times, for example, and with RhCl
33H
2O and TPPTS are reaction raw materials, according to method provided by the invention preparation three [three (-sodium sulfonate phenyl) phosphine] carbonyl hydrogenation Rh, 70～90 ℃ of temperature of reaction, hydrogen and carbon monoxide mol ratio are under 0.6～3.0 the condition in the gas mixture, total reaction time only is 3 hours 50 minutes to 5 hours 30 minutes, and the yield of three [three (-sodium sulfonate phenyl) phosphines] carbonyl hydrogenation Rh can reach 78.9～91.8 heavy %.Method provided by the invention in addition also has raw material and is easy to get, advantage simple to operate, the large-scale industrialization production of [three (-sulfonate phenyl) phosphine] carbonyl hydrogenation Rh that is suitable for three.
The following examples will the present invention will be further described, but not thereby limiting the invention.
Example 1
With 0.1 gram RhCl
33H
2O (chemical pure, Kunming Institute of Precious Metals's product) is dissolved in 3 milliliters of dehydrated alcohol (chemical pure, Chengdu chemical reagent factory produces) in, place and cross 50 milliliters of three-necked bottles of three times with nitrogen replacement, flow velocity with 10 ml/min feeds carbon monoxide (purity 99.9 body %, southwest chemical research institute produces) gas, be warming up to 78 ℃, under agitation reacted 25 minutes, the solution becomes yellowly drips 0.72 gram TPPTS (95 heavy %, self-control) is dissolved in the solution that 3 ml waters obtain, switching flow velocity is 12 ml/min, hydrogen and carbon monoxide mol ratio are 1.2: 1 the hydrogen and the gas mixture of carbon monoxide, with 1N aqueous sodium hydroxide solution conditioned reaction liquid pH value to 12, continue reaction 5 hours, be cooled to 20 ℃, add 40 milliliters of dehydrated alcohols, separate out yellow mercury oxide, filter, be precipitated to neutrality with absolute ethanol washing, in 70 ℃ of vacuum-dryings 4 hours, get yellow solid 0.64 gram
31The PNMR analytical results shows that TPPTS and rhodium have formed coordination, and the FTIR analytical results shows that carbon monoxide and rhodium have formed coordination, and the ICP measurement result shows, this product be three [three (-sodium sulfonate phenyl) phosphine] a carbonyl hydrogenation Rh RhH (CO) (TPPTS)
3, yield 91.8 heavy %.
Example 2
With 0.1 gram RhCl
33H
2O is dissolved in 4 ml methanol, place and cross 50 milliliters of three-necked bottles of three times with nitrogen replacement, flow velocity with 10 ml/min feeds carbon monoxide, be warming up to 78 ℃, under agitation reacted 30 minutes, the solution becomes yellowly, drip 0.8 gram TPPTS and be dissolved in the solution that 3 ml waters obtain, switching flow velocity is 12 ml/min, hydrogen and carbon monoxide mol ratio are 0.6: 1 the hydrogen and the gas mixture of carbon monoxide, and the pH value to 10 with 1N aqueous sodium hydroxide solution conditioned reaction liquid continues reaction 5 hours, cooling, repeat example 1 described separation method, three [three (-sodium sulfonate phenyl) phosphine] carbonyl hydrogenation Rh 0.6 gram, yield 86 heavy %.
Example 3
With 0.2 gram RhCl
33H
2O is dissolved in 3 milliliters of dehydrated alcohols, place and cross 50 milliliters of three-necked bottles of three times with nitrogen replacement, flow velocity with 10 ml/min feeds carbon monoxide, be warming up to 90 ℃, under agitation reacted 30 minutes, the solution becomes yellowly, drip 1.4 gram TPPTS and be dissolved in the solution that 1.6 ml waters obtain, switching flow velocity is 12 ml/min, hydrogen and carbon monoxide mol ratio are the pH value to 12 of the gas mixture of 3.0: 1.0 hydrogen and carbon monoxide with 1N aqueous sodium hydroxide solution conditioned reaction liquid, continue reaction 4 hours, be cooled to 15 ℃, mix with 80 milliliters of dehydrated alcohols, filter the yellow mercury oxide separate out and be precipitated to neutrality, in 70 ℃ of vacuum-dryings 4 hours with absolute ethanol washing, yellow solid three [three (-sodium sulfonate phenyl) phosphine] carbonyl hydrogenation Rh 1.22 grams, yield 87 heavy %.
Example 4
With 0.2 gram RhCl
33H
2O is dissolved in 1 milliliter of dehydrated alcohol, place and cross 50 milliliters of three-necked bottles of three times with nitrogen replacement, flow velocity with 10 ml/min feeds carbon monoxide, be warming up to 70 ℃, under agitation reacted 50 minutes, the solution becomes yellowly, drip 1.5 gram TPPTS and be dissolved in the solution that 10 ml waters obtain, switching flow velocity is 12 ml/min, hydrogen and carbon monoxide mol ratio are 3.0: 1.0 the hydrogen and the gas mixture of carbon monoxide, pH value to 9 with 1N aqueous sodium hydroxide solution conditioned reaction liquid, continue reaction 3 hours, be cooled to 15 ℃, mix with 100 milliliters of dehydrated alcohols, the yellow mercury oxide that filtration is separated out also is precipitated to neutrality with absolute ethanol washing, in 70 ℃ of vacuum-dryings 4 hours, yellow solid three [three (-sodium sulfonate phenyl) phosphine] carbonyl hydrogenation Rh 1.10 grams, yield 78.9 heavy %.
Claims (10)
1. the preparation method of one kind three [three (-sulfonate phenyl) phosphine] carbonyl hydrogenation Rh, it is characterized in that it is included in the alcoholic solution of the compound that under 60～100 ℃ the temperature of reaction carbon monoxide is fed rhodium reacted 10～60 minutes, drip and the mol ratio of rhodium is three (-sulfonate phenyl) phosphine aqueous solution of 3.0～6.0, pH value to 8～14 of conditioned reaction liquid, feed hydrogen and carbon monoxide mol ratio and be 0.1～5.0 the hydrogen and the gas mixture of carbon monoxide and reacted the Separation and Recovery product 2～6 hours.
2. method according to claim 1 is characterized in that in the halogenide of compound selected from rhodium of described rhodium one or more.
3. method according to claim 2, the halogenide that it is characterized in that described rhodium refers to the muriate of rhodium.
4. according to each described method in the claim 1 to 3, it is characterized in that described alcohol is selected from one or more in methyl alcohol, ethanol, propyl alcohol-1, propyl alcohol-2, butanols-1, the butanols-2.
5. method according to claim 4 is characterized in that described pure nail alcohol or ethanol or their mixture.
6. according to each described method in the claim 1 to 3, the concentration that it is characterized in that described rhodium compound alcoholic solution is 0.08～0.80 mol, and the concentration of three (-sulfonate phenyl) phosphine aqueous solution is 0.18～1.70 mol.
7. according to each described method in the claim 1 to 3, it is characterized in that in described three (-sulfonate phenyl) phosphine (-sulfonic acid lithium phenyl) phosphine, three that is selected from three (-sodium sulfonate phenyl) phosphine, three (-potassium sulfonate phenyl) phosphine, three (-sulfonic acid rubidium phenyl) phosphine, three (-sulfonic acid caesium phenyl) phosphine, three (-ammonium sulphonate phenyl) phosphine one or more.
8. method according to claim 7 is characterized in that described three (-sulfonate phenyl) phosphine refers to three (a yellow soda ash phenyl) phosphine.
9. according to each described method in the claim 1 to 3, it is characterized in that the mol ratio of hydrogen and carbon monoxide is 0.5～3.0 in described hydrogen and the carbon mono oxide mixture.
10. according to each described method in the claim 1 to 3, it is characterized in that the mol ratio of described three (-sulfonate phenyl) phosphine and rhodium is 3.0～4.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96120649 CN1046533C (en) | 1996-11-15 | 1996-11-15 | Process for preparing rhodium 3[3 (meta-sulfonate phenyl) phosphine] -carbonyl hydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96120649 CN1046533C (en) | 1996-11-15 | 1996-11-15 | Process for preparing rhodium 3[3 (meta-sulfonate phenyl) phosphine] -carbonyl hydride |
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| Publication Number | Publication Date |
|---|---|
| CN1182745A CN1182745A (en) | 1998-05-27 |
| CN1046533C true CN1046533C (en) | 1999-11-17 |
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| CN102030781B (en) * | 2010-11-09 | 2013-11-27 | 中国海洋石油总公司 | Preparation method for acetylacetonatodicarbonyl rhodium |
| CN102351912B (en) * | 2011-10-25 | 2014-11-05 | 中国海洋石油总公司 | Preparation method of tris[tri(3-sodium sulfonate-phenyl)phosphine]rhodium carbonylhydride |
| CN105618145B (en) * | 2014-11-07 | 2017-11-07 | 中国石油天然气股份有限公司 | A kind of preparation method of three [three (a sodium sulfonate phenyl) phosphines] chlorination rhodium catalysts |
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1996
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