CN1179429A - Process for preparing rhodium tri [tri (meta-sulfonate phenyl) phosphine] monochloro monocarbonyl - Google Patents
Process for preparing rhodium tri [tri (meta-sulfonate phenyl) phosphine] monochloro monocarbonyl Download PDFInfo
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- CN1179429A CN1179429A CN 96120056 CN96120056A CN1179429A CN 1179429 A CN1179429 A CN 1179429A CN 96120056 CN96120056 CN 96120056 CN 96120056 A CN96120056 A CN 96120056A CN 1179429 A CN1179429 A CN 1179429A
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- phosphine
- phenyl
- sulfonate phenyl
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- sulfonate
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Abstract
A process for preparing 2 [3 (meta-sulfonate phenyl) phosphine] -chloro -carbonyl rhodium includes such steps as introduction of CO to alcoholic solution of rhodium chloride at 60-100 deg. C, reaction for 10-60 min, dripping in 3 (meta -sulfonate phenyl) phosphine aqueousolution, continue reaction for 20-60 min, and separating product, and features easily available raw materials, simple process, and high output rate and quality of product.
Description
The invention relates to the preparation method of the organic compound that contains periodic table of elements group VIII element, more particularly, is the preparation method of [three (-sulfonate phenyl) phosphine] chlorine one rhodium carbonyl about two.
Two [three (-sulfonate phenyl) phosphine] chlorine one rhodium carbonyl has good catalytic activity and selectivity to the reaction of preparing aldehyde by hydro formylating defin in the profit two-phase system.According to US 5,057, disclosed two in 618 [preparation method of three (-sodium sulfonate phenyl) phosphine one chlorine one rhodium carbonyl is with RhCl (TPPTS)
39H
2O[is TPPTS (-sodium sulfonate phenyl) phosphine that refers to three wherein] be dissolved in in the water of nitrification, fed carbon monoxide 10 minutes, through separating and purifying [three (-sodium sulfonate phenyl) phosphine] chlorine one rhodium carbonyl [Rh (CO) Cl (TPPTS) that can obtain two
26H
2O], its yield can reach 95 heavy % (with reference to example 13), but raw materials used RhCl (TPPTS)
39H
2O need use RhCl
33H
2O and TTTPS react and make, and its yield only is 73 heavy % (with reference to example 9), if promptly with RhCl
33H
2O is that starting raw material calculates, and the yield of two [three (-sodium sulfonate phenyl) phosphine] chlorine one rhodium carbonyl only has less than 70 heavy %, and preparation process was divided into for two steps and carries out complicated operation.Also disclose another kind of in this patent with [Rh (μ-Cl) (CO)
2]
2Be the preparation method of raw material, that is: toward [Rh (μ-Cl) (CO)
2]
2Toluene solution in add the aqueous solution of TPPTS, react separable Rh (CO) Cl (TPPS) of going out after 15 minutes
26H
2O, its yield also can reach 84 heavy %, but this preparation method carries out equally in two steps, raw materials used [Rh (μ-Cl) (CO)
2]
2Need use RhCl equally
33H
2The O preparation, and preparation process is more complicated.
Purpose of the present invention promptly is that the shortcoming that overcomes above-mentioned prior art for preparing process complexity provides a kind of new, the preparation method of preparation process simple two [three (-sulfonate phenyl) phosphine] chlorine one rhodium carbonyl.
Method provided by the invention is included in 60～100 ℃ and carbon monoxide fed in the muriatic alcoholic solution of rhodium reacted 10～60 minutes, dripping mol ratio with rhodium and be three (-sulfonate phenyl) phosphine of 1.9～4.0] aqueous solution continues to react 20～60 minutes, separated product two [three (-the sulfonate phenyl) phosphine] chlorine one rhodium carbonyl.
Alcohol in the described rhodium muriate alcoholic solution is selected from one or more in the alcohol that is in liquid state under described reaction conditions, comprises 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; With the amylalcohol of two above hydroxyls, hexanol, hexalin, phenylcarbinol, phenylethyl alcohol etc.One or more in particular methanol, ethanol, propyl alcohol-1, propyl alcohol-2, butanols-1, the butanols-2 wherein, more particular methanol or ethanol or their mixture can contain 2 heavy % with interior water in the described alcoholic solution.
The concentration of the muriatic alcoholic solution of described rhodium or three (-sulfonate phenyl) the phosphine aqueous solution can change to the scope of its saturated solution at rarer solution, but the amount of the solvent that uses was too big when solution was too rare, thus preferred 0.08 mol of the concentration of the muriate alcoholic solution of rhodium to preferred 0.18 mol of concentration of saturated solution, more preferred 0.08～0.8 mol three (-sulfonate phenyl) the phosphine aqueous solution to saturated solution, more preferred 0.18～1.76 mol.The mol ratio preferred 1.95～3.0 of described three (-sulfonate phenyl) phosphine and rhodium.
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, more preferred three (-the sodium sulfonate phenyl) phosphine, in three (-potassium sulfonate phenyl) phosphine, three (-ammonium sulphonate phenyl) phosphine one or more, preferably three (-sodium sulfonate phenyl) phosphine is TPPTS.
The separation of described product two [three (-sulfonate phenyl) phosphine] chlorine one rhodium carbonyl can be adopted US5, and method described in 057,618 is separated and purifying with chromatographic column; Also can in reacted product, add excessive alcohol, and be cooled to 10～25 ℃ and make two [three (-sulfonate phenyl) phosphine] chlorine one rhodium carbonyl and separate out, dry under washing, the vacuum after filtration, obtain two [three (-the sulfonate phenyl) phosphine] chlorine one rhodium carbonyl.
Method provided by the invention has following advantage:
(1) simple, the raw material of preparation process is easy to get.Method provided by the invention is directly with the muriate such as the RhCl of rhodium
3Be raw material, a step promptly can be made into two [three (-sulfonate phenyl) phosphine] chlorine one rhodium carbonyl overcome the defective that separating for several times must be carried out and must be carried out to prior art in two steps, and reaction conditions is comparatively gentle, and post-reaction treatment is convenient.
(2) yield height, good product quality.Adopt method provided by the invention, the yield of product two [three (-sulfonate phenyl) phosphine] chlorine one rhodium carbonyl is higher, for example, and with RhCl
33H
2O and TPPTS are that reaction raw materials preparation two [three (-sodium sulfonate phenyl) phosphine] its yield of a chlorine one rhodium carbonyl can reach more than the 70 heavy %, even can be up to 95.0 heavy %, and purity is good, does not need through recrystallization purifying, and this is that prior art is beyond one's reach, and uses
31The result that PNMR measures product shows, do not contain each TPPTS and oxide compound of network not in the product.
The following examples will the present invention will be further described, but not thereby limiting the invention.
Example 1
With 1.0 gram RhCl
33H
2O (chemical pure, Kunming Institute of Precious Metals's product) is dissolved in 20 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 15 ml/min feeds carbon monoxide (purity 99.9 body %, southwest chemical research institute produces) gas, and being warming up to 78 ℃, back flow reaction 50 minutes stops heating, Dropwise 5 .0 gram three (-the sodium sulfonate phenyl) phosphine (95 heavy %, self-control) is dissolved in the solution that 10 ml waters are made into, continues, cool off and add 40 milliliters of dehydrated alcohols 78 ℃ of back flow reaction 40 minutes, continue to be cooled to 20 ℃ of filtrations, extremely neutral with the yellow mercury oxide that washing with alcohol obtains, in 80 ℃, drying under reduced pressure 4 hours, get faint yellow solid 4.7 grams
31The analytical results of PNMR shows that TPPTS and rhodium have formed coordination FTIR analytical results and shown that carbon monoxide and rhodium have formed coordination ICP measurement result and shown, this product be two [three (-sodium sulfonate phenyl) phosphine) chlorine one rhodium carbonyl RhCl (CO) (TPPTS)
2, yield 95 heavy %.
Example 2
With 0.1 gram RhCl
33H
2O is dissolved in 3 ml methanol (chemical pure, Chengdu chemical reagent factory produces) in, place and cross 25 milliliters of three-necked bottles of three times with nitrogen replacement, feed CO (carbon monoxide converter) gas with the flow velocity of 15 ml/min, and be warming up to 90 ℃, back flow reaction 50 minutes, stop heating, drip 0.43 gram TPPTS and be dissolved in the solution that 2 ml waters are made into, continue 90 ℃ of back flow reaction 40 minutes, repeat example 1 described separation method, two [three (-sodium sulfonate phenyl) phosphines] chlorine one rhodium carbonyl RhCl (CO) (TPPTS)
20.37 gram, yield 75.0 heavy %.
Example 3
With 0.1 gram RhCl
33H
2O is dissolved in 3 milliliters of dehydrated alcohols, place and cross 25 milliliters of three-necked bottles of three times with nitrogen replacement, flow velocity with 15 ml/min feeds CO (carbon monoxide converter) gas, be warming up to 80 ℃, back flow reaction 50 minutes stops heating, drip 0.64 gram TPPTS and be dissolved in the solution that 3 ml waters are made into, continuation repeats example 1 described separation method 80 ℃ of back flow reaction 40 minutes, two [three (-sodium sulfonate phenyl) phosphines] chlorine one rhodium carbonyl RhCl (CO) (TPPTS)
20.4 gram, yield 80.9 heavy %.
Example 4
With 0.5 gram RhCl
33H
2O is dissolved in 2.5 milliliters of dehydrated alcohols, place and cross 25 milliliters of three-necked bottles of three times with nitrogen replacement, flow velocity with 15 ml/min feeds CO (carbon monoxide converter) gas, be warming up to 60 ℃, reacted 20 minutes, drip 2.5 gram TPPTS and be dissolved in the solution that 4.0 ml waters are made into, be warming up to 80 ℃ and continue reaction 20 minutes, cooling, and add 25 milliliters of dehydrated alcohols, continue to be cooled to 20 ℃, filter, extremely neutral with the yellow mercury oxide that washing with alcohol obtains, in 80 ℃, drying under reduced pressure 4 hours, two [three (-sodium sulfonate phenyl) phosphines] chlorine one rhodium carbonyl RhCl (CO) (TPPTS)
21.80 gram, yield 72.8 heavy %.
Claims (8)
1. the preparation method of one kind two [three (-sulfonate phenyl) phosphine] chlorine one rhodium carbonyl, it is characterized in that it is included in 60～100 ℃ and carbon monoxide fed in the muriatic alcoholic solution of rhodium reacted 10～60 minutes, dripping mol ratio with rhodium and be three (-sulfonate phenyl) phosphine of 1.9～4.0] aqueous solution continues to react the Separation and Recovery product 20～60 minutes.
2. according to the described method of claim 1, it is characterized in that described alcohol is selected from methyl alcohol, ethanol, propyl alcohol-1, propyl alcohol-2, butanols-1, one or more in the butanols-2.
3. according to the described method of claim 2, it is characterized in that described pure nail alcohol or ethanol or their mixture.
4. according to claim 1 or 2 described methods, the concentration that it is characterized in that the muriatic alcoholic solution of described rhodium is 0.08～0.8 mol, and the concentration of three (-sulfonate phenyl) phosphine aqueous solution is 0.18～1.76 mol.
5. according to claim 1 or 2 described methods, it is characterized in that the mol ratio of described three (-sulfonate phenyl) phosphine and rhodium is 1.95～3.0.
6. according to claim 1 or 2 described methods, it is characterized in that described three (-sulfonate phenyl) phosphine (-sulfonic acid lithium phenyl) phosphine that is selected from three, three (-sodium sulfonate phenyl) phosphine, one or more in three (-potassium sulfonate phenyl) phosphine, three (-sulfonic acid rubidium phenyl) phosphine, three (-sulfonic acid caesium phenyl) phosphine, three (-ammonium sulphonate phenyl) phosphine.
7. according to the described method of claim 6, it is characterized in that in described three (-sulfonate phenyl) phosphine (-sodium sulfonate phenyl) phosphine, three that is selected from three (-potassium sulfonate phenyl) phosphine, three (-ammonium sulphonate phenyl) phosphine one or more.
8. according to the described method of claim 7, it is characterized in that described three (-sulfonate phenyl) phosphine (-sodium sulfonate phenyl) phosphine that refers to three.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120056A CN1046532C (en) | 1996-10-15 | 1996-10-15 | Process for preparing rhodium tri [tri (meta-sulfonate phenyl) phosphine] monochloro monocarbonyl |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120056A CN1046532C (en) | 1996-10-15 | 1996-10-15 | Process for preparing rhodium tri [tri (meta-sulfonate phenyl) phosphine] monochloro monocarbonyl |
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|---|---|
| CN1179429A true CN1179429A (en) | 1998-04-22 |
| CN1046532C CN1046532C (en) | 1999-11-17 |
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| CN113121614A (en) * | 2021-04-22 | 2021-07-16 | 中国科学院上海高等研究院 | Water-soluble metal-based complex and preparation method and application thereof |
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|---|---|---|---|---|
| CN102391313A (en) * | 2011-10-25 | 2012-03-28 | 中国海洋石油总公司 | Preparation method of 2-[3-(3-sodium sulfonylphenyl)phosphinyl] carbonyl rhodium chlorine |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| HUT52104A (en) * | 1988-12-02 | 1990-06-28 | Hoechst Ag | Process for producing complex compounds comprising sulfonated phenyl phosphanes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113121614A (en) * | 2021-04-22 | 2021-07-16 | 中国科学院上海高等研究院 | Water-soluble metal-based complex and preparation method and application thereof |
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