CN114591373B - Preparation method of acetyl acetone triphenylphosphine rhodium carbonyl - Google Patents
Preparation method of acetyl acetone triphenylphosphine rhodium carbonyl Download PDFInfo
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- CN114591373B CN114591373B CN202210262699.3A CN202210262699A CN114591373B CN 114591373 B CN114591373 B CN 114591373B CN 202210262699 A CN202210262699 A CN 202210262699A CN 114591373 B CN114591373 B CN 114591373B
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- rhodium
- triphenylphosphine
- carbonyl
- acetylacetonate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000010992 reflux Methods 0.000 claims abstract description 43
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000012065 filter cake Substances 0.000 claims abstract description 32
- 239000000047 product Substances 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 21
- BDDWSAASCFBVBK-UHFFFAOYSA-N rhodium;triphenylphosphane Chemical compound [Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BDDWSAASCFBVBK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 19
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims abstract description 17
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910003450 rhodium oxide Inorganic materials 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 150000002192 fatty aldehydes Chemical class 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 43
- 239000010948 rhodium Substances 0.000 claims description 31
- 229910052703 rhodium Inorganic materials 0.000 claims description 30
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 8
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 6
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 claims description 6
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 6
- ICFKJAPZLCYFIA-UHFFFAOYSA-N [Rh].[C]=O.c1ccc(cc1)P(c1ccccc1)c1ccccc1 Chemical compound [Rh].[C]=O.c1ccc(cc1)P(c1ccccc1)c1ccccc1 ICFKJAPZLCYFIA-UHFFFAOYSA-N 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 239000000460 chlorine Substances 0.000 abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 abstract description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 4
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- -1 rhodium organic compound Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006170 formylation reaction Methods 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- QRSFFHRCBYCWBS-UHFFFAOYSA-N [O].[O] Chemical compound [O].[O] QRSFFHRCBYCWBS-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000022244 formylation Effects 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RTRUQNOXAPOHJF-UHFFFAOYSA-N pentane-2,4-dione;rhodium;(triphenyl-$l^{5}-phosphanylidene)methanone Chemical compound [Rh].CC(=O)CC(C)=O.C=1C=CC=CC=1P(C=1C=CC=CC=1)(=C=O)C1=CC=CC=C1 RTRUQNOXAPOHJF-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0073—Rhodium compounds
- C07F15/008—Rhodium compounds without a metal-carbon linkage
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of rhodium acetylacetonate triphenylphosphine carbonyl, which comprises the steps of stirring and mixing rhodium oxide and acetylacetone, adding an initiator, heating to a reflux temperature for reaction, continuously reacting fatty aldehyde of triphenylphosphine after a system turns into brown yellow from black at the reflux temperature, adding deionized water after cooling after the reaction is finished, filtering, washing a filter cake by the deionized water, and vacuum drying the filter cake to obtain the rhodium acetylacetonate triphenylphosphine carbonyl. The preparation method can prepare the triphenylphosphine rhodium carbonyl acetylacetonate with low chlorine impurity content, which causes catalyst poisoning, and meanwhile, because acetylacetone is both a reactant and a solvent in the reaction, side reaction is reduced, and the obtained triphenylphosphine rhodium carbonyl acetylacetonate product has high yield and purity, does not need repeated washing, and can be directly applied after drying.
Description
Technical Field
The invention relates to the field of noble metal catalyst synthesis, in particular to a preparation method of acetyl acetone triphenylphosphine rhodium carbonyl.
Background
Rhodium catalyst is an important catalytic material and has been widely used in petrochemical industry, pharmaceutical chemical industry, fine chemical industry, environmental protection and other fields for recent 30 years.
Rhodium acetylacetonate triphenylphosphine carbonyl with the molecular formula Rh (C) 5 H 7 O 2 )(CO)(PPh 3 ) The method is characterized by being a chelate rhodium organic compound coordinated by oxygen-oxygen ligand, having higher activity, higher selectivity and normal isomerism ratio for hydroformylation of some olefins, relatively mild reaction condition and less side reaction, and being a main catalyst adopted by the current low-pressure oxo synthesis method.
The triphenylphosphine rhodium carbonyl acetylacetonate is generally prepared from water and rhodium trichloride as raw materials. According to the preparation method of the triphenylphosphine rhodium carbonyl acetylacetonate disclosed in CN106674285B, a toluene solution of rhodium trichloride is taken as a reaction system, carbon monoxide is taken as a carbonyl source, and triphenylphosphine is finally added to synthesize a target product. The preparation method of the patent has the advantages of high rhodium single pass conversion rate, simple and convenient process and mild conditions. However, the chlorine ions introduced from the reaction raw materials cannot be completely removed, so that the catalytic activity of the final product is affected. According to the preparation method disclosed in J.chem.Soc.,1964,3156-3159, dichloro-tetracarbonyl-rhodium and acetylacetone are used as raw materials, petroleum ether is used as a solvent, sodium carbonate is added as an auxiliary agent, triphenylphosphine is added, and after a period of up to one week at reflux temperature, the product is obtained, and the yield of rhodium metal in the raw material dichloro-tetracarbonyl-rhodium is 79%. The method can prepare the triphenylphosphine rhodium carbonyl acetylacetonate from the reaction of the dichloro-tetracarbonyl rhodium, but the method has long reaction time and low product yield, and meanwhile, the product has low catalytic activity and long service life due to high chloride ion content.
According to the method, a chlorine-containing rhodium compound is used as a starting material, a large amount of chloride ions are introduced into a reaction system, and due to incomplete reaction of part of the raw materials and strong charge adsorption of the chloride ions and rhodium, a large amount of chloride ions are easily introduced into a target product of the triphenylphosphine carbonyl rhodium acetylacetonate, so that the catalyst activity is low when the triphenylphosphine carbonyl rhodium acetylacetonate is used as an olefin formylation reaction, and the catalyst is poisoned when serious. Therefore, a large amount of water is required to wash chloride ions in the subsequent washing process to meet the product standards. Although the yield of the acetyl acetone carbonyl triphenylphosphine rhodium is improved to a certain extent through technical improvement and condition control, the catalytic activity-free rhodium black is easily introduced and the chloride ions exceed the standard due to long reaction period and harsh reaction conditions, the intermediate product is recrystallized by using an organic solvent, and the product is treated by repeatedly washing with a large amount of water.
In addition, a large number of domestic and foreign patents clearly indicate that chlorine can cause rhodium carbonyl poisoning of triphenylphosphine carbonyl of acetylacetone. There are reports of olefin conversion rate reduction and even catalyst poisoning caused by standard exceeding of chloride ions in olefin formylation devices at home and abroad. Rhodium is extremely rare in distribution in the crust, difficult to mine and enrich, high in cost, and is the most expensive metal of platinum group metals, and the rhodium recovery and refining cost is high due to the special chemical property of rhodium. Therefore, the preparation of the triphenylphosphine rhodium carbonyl acetylacetonate with high yield and high purity is of great significance.
Disclosure of Invention
The invention aims at solving the technical problems of low yield and high chlorine content of products in the preparation process of the triphenylphosphine rhodium carbonyl acetylacetonate, and provides a preparation method of the triphenylphosphine rhodium carbonyl acetylacetonate with high yield and low chlorine content.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
step one, mixing: in a three-neck flask with a reflux condenser, rhodium oxide and acetylacetone solution are stirred and mixed uniformly, a water ring type vacuum pump is used, the mixture is continuously pumped out under the vacuum degree of-0.08 Mpa, and nitrogen with the pressure of 0.02Mpa is injected for three times, so that the oxygen content in the three-neck flask is less than 1000ppm, and the generation of byproducts caused by the overhigh oxygen content is prevented, and the purity of the product is reduced; the rhodium content in the rhodium oxide is 82.5%; the mass ratio of the acetylacetone solution to rhodium is 6-10;
step two, reflux: adding an initiator into the mixed solution prepared in the step one, refluxing and stirring for 1.5 hours at the temperature of 120-140 ℃, adding a fatty aldehyde solution dissolved with triphenylphosphine to continuously react at the reflux temperature of 120-140 ℃ after the solution turns to brown from black, stirring and reacting for 1.5 hours, stopping heating and cooling to room temperature; the initiator is ammonia water, and the addition amount of the ammonia water is 1ml;
step three, filtering and washing: adding deionized water into the solution prepared in the second step to separate out the triphenylphosphine rhodium carbonyl acetylacetonate from an acetylacetone organic phase, filtering to obtain a filter cake, and washing the filter cake with deionized water to remove impurities;
step four, drying: vacuum drying the filter cake in the third step to obtain acetyl acetone triphenylphosphine rhodium carbonyl;
the purity of the acetyl acetone triphenylphosphine rhodium carbonyl is more than 99.9%, the chloride ion content is 1.4-1.7ppm, and the yield is 96.5-97.4%.
Preferably, in the second step, the fatty aldehyde is selected from one of acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde and hexanal, and the mass ratio of the fatty aldehyde to rhodium is 0.5-2.
Preferably, in the second step, the mass ratio of triphenylphosphine to rhodium is 2.8-3.8.
Preferably, in the third step, the mass ratio of deionized water to acetylacetone is 0.5.
Preferably, in the fourth step, the vacuum drying temperature is 30 ℃ and the vacuum degree is-0.06 MPa.
Compared with the prior art, the invention has the following advantages:
1. the acetylacetone and the fatty aldehyde are used as reactants and solvents, no other solvents are introduced into the reaction system, and the anhydrous reagent is used, so that the generation of byproducts is reduced, the product yield is improved, and the product purity is improved;
2. the rhodium raw material without chloride ions is adopted, so that no chlorine source is introduced in the whole reaction process, the triphenylphosphine rhodium carbonyl acetylacetonate with low chlorine content is obtained, and the dried rhodium is directly applied to olefin oxo synthesis, and the chlorine removal procedures of intermediate recrystallization, repeated product washing and the like are omitted.
Drawings
FIG. 1 is a process flow diagram of a process for preparing triphenylphosphine rhodium carbonyl acetylacetonate in accordance with the present invention;
FIG. 2 is an infrared spectrum of triphenylphosphine rhodium carbonyl acetylacetonate prepared in accordance with the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
A preparation method of acetyl acetone triphenylphosphine rhodium carbonyl comprises the following steps:
step one, mixing: in a three-neck flask with a reflux condenser, 0.122g of rhodium oxide with rhodium content of 0.1g is dissolved in 0.6g of acetylacetone solution, and after stirring and mixing uniformly, a water ring type vacuum pump is used for continuously evacuating under the vacuum degree of-0.08 Mpa and injecting nitrogen with pressure of 0.02Mpa for three times, so that the oxygen content in the three-neck flask is less than 1000ppm;
step two, reflux: adding 1ml of ammonia water into the mixed solution prepared in the step one, heating to 120 ℃, stirring for 1.5 hours at a reflux temperature, injecting 0.28g of triphenylphosphine and 0.05 g of anaerobic acetaldehyde after the solution turns to brown yellow from black, continuously carrying out reflux reaction at 120 ℃, stirring for 1.5 hours, stopping heating, and cooling the solution to room temperature;
step three, filtering and washing: adding 0.3g of deionized water into the solution prepared in the step two, fully stirring until yellow solid is separated out from the mixed solution, filtering to obtain a filter cake, and washing the filter cake with deionized water again to remove impurities;
step four, drying: drying the filter cake obtained in the step three at 30 ℃ and a vacuum degree of minus 0.06 MPa to obtain an acetyl acetone triphenylphosphine rhodium carbonyl product;
the purity of the acetyl acetone triphenylphosphine rhodium carbonyl is more than 99.9%, the chloride ion content is 1.6ppm, and the yield is 97.3%.
Example 2
A preparation method of acetyl acetone triphenylphosphine rhodium carbonyl comprises the following steps:
step one, mixing: dissolving 0.122g of rhodium oxide with rhodium content of 0.1g in 1g of acetylacetone solution in a three-neck flask with a reflux condenser, stirring and mixing uniformly, continuously evacuating under vacuum degree of-0.08 Mpa by using a water ring vacuum pump, and injecting nitrogen with pressure of 0.02Mpa for three times to realize that the oxygen content in the three-neck flask is less than 1000ppm;
step two, reflux: adding 1ml of ammonia water into the mixed solution prepared in the step one, heating to 120 ℃, stirring for 1.5 hours at a reflux temperature, injecting 0.31g of triphenylphosphine and 0.08 g of anaerobic acetaldehyde once after the solution turns to brown from black, continuing to reflux and react at 120 ℃, stirring and reacting for 1.5 hours, stopping heating, and cooling the solution to room temperature;
step three, filtering and washing: adding 0.5g of deionized water into the solution prepared in the second step, fully stirring until yellow solid is separated out from the mixed solution, filtering to obtain a filter cake, and washing the filter cake with deionized water again to remove impurities;
step four, drying: drying the filter cake obtained in the step three at 30 ℃ and a vacuum degree of minus 0.06 MPa to obtain an acetyl acetone triphenylphosphine rhodium carbonyl product;
the purity of the acetyl acetone triphenylphosphine rhodium carbonyl is more than 99.9%, the chloride ion content is 1.7ppm, and the yield is 96.6%.
Example 3
A preparation method of acetyl acetone triphenylphosphine rhodium carbonyl comprises the following steps:
step one, mixing: dissolving 0.122g of rhodium oxide with rhodium content of 0.1g in 1g of acetylacetone solution in a three-neck flask with a reflux condenser, stirring and mixing uniformly, continuously evacuating under vacuum degree of-0.08 Mpa by using a water ring vacuum pump, and injecting nitrogen with pressure of 0.02Mpa for three times to realize that the oxygen content in the three-neck flask is less than 1000ppm;
step two, reflux: adding 1ml of ammonia water into the mixed solution prepared in the step one, heating to 120 ℃, stirring for 1.5 hours at a reflux temperature, injecting 0.38g of triphenylphosphine and 0.2 g of anaerobic propanal at one time after the solution turns to brown yellow from black, continuing to reflux and react at 120 ℃, stirring and reacting for 1.5 hours, stopping heating, and cooling the solution to room temperature;
step three, filtering and washing: adding 0.5g of deionized water into the solution prepared in the second step, fully stirring until yellow solid is separated out from the mixed solution, filtering to obtain a filter cake, and washing the filter cake with deionized water again to remove impurities;
step four, drying: drying the filter cake obtained in the step three at 30 ℃ and a vacuum degree of minus 0.06 MPa to obtain an acetyl acetone triphenylphosphine rhodium carbonyl product;
the purity of the acetyl acetone triphenylphosphine rhodium carbonyl is more than 99.9%, the chloride ion content is 1.6ppm, and the yield is 96.5%.
Example 4
A preparation method of acetyl acetone triphenylphosphine rhodium carbonyl comprises the following steps:
step one, mixing: in a three-neck flask with a reflux condenser, 0.122g of rhodium oxide with rhodium content of 0.1g is dissolved in 0.9g of acetylacetone solution, and after stirring and mixing uniformly, a water ring type vacuum pump is used for continuously evacuating under the vacuum degree of-0.08 Mpa and injecting nitrogen with pressure of 0.02Mpa for three times, so that the oxygen content in the three-neck flask is less than 1000ppm;
step two, reflux: adding 1ml of ammonia water into the mixed solution prepared in the step one, heating to 120 ℃, stirring for 1.5 hours at a reflux temperature, injecting 0.30g of triphenylphosphine and 0.12 g of anaerobic butyraldehyde once after the solution turns to brown from black, continuing to reflux and react at 120 ℃, stirring and reacting for 1.5 hours, stopping heating, and cooling the solution to room temperature;
step three, filtering and washing: adding 0.45g of deionized water into the solution prepared in the second step, fully stirring until yellow solid is separated out from the mixed solution, filtering to obtain a filter cake, and washing the filter cake with deionized water again to remove impurities;
step four, drying: drying the filter cake obtained in the step three at 30 ℃ and a vacuum degree of minus 0.06 MPa to obtain an acetyl acetone triphenylphosphine rhodium carbonyl product;
the purity of the acetyl acetone triphenylphosphine rhodium carbonyl is more than 99.9%, the chloride ion content is 1.4ppm, and the yield is 97.1%.
Example 5
A preparation method of acetyl acetone triphenylphosphine rhodium carbonyl comprises the following steps:
step one, mixing: in a three-neck flask with a reflux condenser, 0.122g of rhodium oxide with rhodium content of 0.1g is dissolved in 0.8g of acetylacetone solution, and after stirring and mixing uniformly, a water ring type vacuum pump is used for continuously evacuating under the vacuum degree of-0.08 Mpa and injecting nitrogen with pressure of 0.02Mpa for three times, so that the oxygen content in the three-neck flask is less than 1000ppm;
step two, reflux: adding 1ml of ammonia water into the mixed solution prepared in the step one, heating to 140 ℃, stirring for 1.5 hours at a reflux temperature, injecting 0.36g of triphenylphosphine and 0.2 g of anaerobic valeraldehyde at one time after the solution turns to brown from black, continuing to reflux and react at 140 ℃, stirring and reacting for 1.5 hours, stopping heating, and cooling the solution to room temperature;
step three, filtering and washing: adding 0.4g of deionized water into the solution prepared in the step two, fully stirring until yellow solid is separated out from the mixed solution, filtering to obtain a filter cake, and washing the filter cake with deionized water again to remove impurities;
step four, drying: drying the filter cake obtained in the step three at 30 ℃ and a vacuum degree of minus 0.06 MPa to obtain an acetyl acetone triphenylphosphine rhodium carbonyl product;
the purity of the acetyl acetone triphenylphosphine rhodium carbonyl is more than 99.9%, the chloride ion content is 1.5ppm, and the yield is 96.7%.
Example 6
A preparation method of acetyl acetone triphenylphosphine rhodium carbonyl comprises the following steps:
step one, mixing: in a three-neck flask with a reflux condenser, 0.122g of rhodium oxide with rhodium content of 0.1g is dissolved in 1.0g of acetylacetone solution, and after stirring and mixing uniformly, a water ring type vacuum pump is used for continuously evacuating under the vacuum degree of-0.08 Mpa and injecting nitrogen with pressure of 0.02Mpa for three times, so that the oxygen content in the three-neck flask is less than 1000ppm;
step two, reflux: adding 1ml of ammonia water into the mixed solution prepared in the step one, heating to 130 ℃, stirring for 1.5 hours at a reflux temperature, injecting 0.3g of triphenylphosphine and 0.2 g of anaerobic hexanal at one time after the solution turns to brown from black, continuing to reflux and react at 130 ℃, stirring and reacting for 1.5 hours, stopping heating, and cooling the solution to room temperature;
step three, filtering and washing: adding 0.5g of deionized water into the solution prepared in the second step, fully stirring until yellow solid is separated out from the mixed solution, filtering to obtain a filter cake, and washing the filter cake with deionized water again to remove impurities;
step four, drying: drying the filter cake obtained in the step three at 30 ℃ and a vacuum degree of minus 0.06 MPa to obtain an acetyl acetone triphenylphosphine rhodium carbonyl product;
the purity of the acetyl acetone triphenylphosphine rhodium carbonyl is more than 99.9%, the chloride ion content is 1.6ppm, and the yield is 97.4%.
Example 7
A preparation method of acetyl acetone triphenylphosphine rhodium carbonyl comprises the following steps:
step one, mixing: in a three-neck flask with a reflux condenser, 0.122g of rhodium oxide with rhodium content of 0.1g is dissolved in 1.0g of acetylacetone solution, and after stirring and mixing uniformly, a water ring type vacuum pump is used for continuously evacuating under the vacuum degree of-0.08 Mpa and injecting nitrogen with pressure of 0.02Mpa for three times, so that the oxygen content in the three-neck flask is less than 1000ppm;
step two, reflux: adding 1ml of ammonia water into the mixed solution prepared in the step one, heating to 135 ℃, stirring for 1.5 hours at a reflux temperature, injecting 0.32g of triphenylphosphine and 0.18 g of anaerobic acetaldehyde once after the solution turns to brown from black, continuing to reflux and react at 135 ℃, stirring and reacting for 1.5 hours, stopping heating, and cooling the solution to room temperature;
step three, filtering and washing: adding 0.5g of deionized water into the solution prepared in the second step, fully stirring until yellow solid is separated out from the mixed solution, filtering to obtain a filter cake, and washing the filter cake with deionized water again to remove impurities;
step four, drying: drying the filter cake obtained in the step three at 30 ℃ and a vacuum degree of minus 0.06 MPa to obtain an acetyl acetone triphenylphosphine rhodium carbonyl product;
the purity of the acetyl acetone triphenylphosphine rhodium carbonyl is more than 99.9%, the chloride ion content is 1.5ppm, and the yield is 97.2%.
Example 8
A preparation method of acetyl acetone triphenylphosphine rhodium carbonyl comprises the following steps:
step one, mixing: in a three-neck flask with a reflux condenser, 0.122g of rhodium oxide with rhodium content of 0.1g is dissolved in 1.0g of acetylacetone solution, and after stirring and mixing uniformly, a water ring type vacuum pump is used for continuously evacuating under the vacuum degree of-0.08 Mpa and injecting nitrogen with pressure of 0.02Mpa for three times, so that the oxygen content in the three-neck flask is less than 1000ppm;
step two, reflux: adding 1ml of ammonia water into the mixed solution prepared in the step one, heating to 135 ℃, stirring for 1.5 hours at a reflux temperature, injecting 0.32g of triphenylphosphine and 0.16 g of anaerobic acetaldehyde once after the solution turns to brown from black, continuing to reflux and react at 135 ℃, stirring and reacting for 1.5 hours, stopping heating, and cooling the solution to room temperature;
step three, filtering and washing: adding 0.5g of deionized water into the solution prepared in the second step, fully stirring until yellow solid is separated out from the mixed solution, filtering to obtain a filter cake, and washing the filter cake with deionized water again to remove impurities;
step four, drying: drying the filter cake obtained in the step three at 30 ℃ and a vacuum degree of minus 0.06 MPa to obtain an acetyl acetone triphenylphosphine rhodium carbonyl product;
the purity of the acetyl acetone triphenylphosphine rhodium carbonyl is more than 99.9%, the chloride ion content is 1.5ppm, and the yield is 97.2%.
The product yields and analytical results are shown in Table 1.
TABLE 1 product yields and analytical results Table
It can be concluded from the data in Table 1 that examples 1 to 8 are the preparation methods of triphenylphosphine rhodium carbonyl acetylacetonate provided by the present invention, and the objective of high yield and low chlorine impurity content of triphenylphosphine rhodium carbonyl acetylacetonate can be obtained.
The spectrogram of the triphenylphosphine rhodium acetylacetonate carbonyl product prepared by the invention is shown in figure 1 by an FT-IR instrument, and is consistent with the standard spectrogram of the triphenylphosphine rhodium acetylacetonate carbonyl disclosed and reported, and the triphenylphosphine rhodium acetylacetonate carbonyl product is determined to be the triphenylphosphine rhodium acetylacetonate carbonyl.
Claims (5)
1. A preparation method of acetyl acetone triphenylphosphine rhodium carbonyl is characterized in that: the method comprises the following steps:
step one, mixing: in a three-neck flask with a reflux condenser, rhodium oxide and acetylacetone solution are stirred and mixed uniformly, a water ring type vacuum pump is used, the mixture is continuously pumped out under the vacuum degree of-0.08 Mpa, and nitrogen with the pressure of 0.02Mpa is injected for three times, so that the oxygen content in the three-neck flask is less than 1000ppm, and the generation of byproducts caused by the overhigh oxygen content is prevented, and the purity of the product is reduced; the rhodium content in the rhodium oxide is 82.5%; the mass ratio of the acetylacetone solution to rhodium is 6-10;
step two, reflux: adding an initiator into the mixed solution prepared in the step one, refluxing and stirring for 1.5 hours at the temperature of 120-140 ℃, adding a fatty aldehyde solution dissolved with triphenylphosphine to continuously react at the reflux temperature of 120-140 ℃ after the solution turns to brown from black, stirring and reacting for 1.5 hours, stopping heating and cooling to room temperature; the initiator is ammonia water, and the addition amount of the ammonia water is 1ml;
step three, filtering and washing: adding deionized water into the solution prepared in the second step to separate out the triphenylphosphine rhodium carbonyl acetylacetonate from an acetylacetone organic phase, filtering to obtain a filter cake, and washing the filter cake with deionized water to remove impurities;
step four, drying: vacuum drying the filter cake in the third step to obtain acetyl acetone triphenylphosphine rhodium carbonyl;
the purity of the acetyl acetone triphenylphosphine rhodium carbonyl is more than 99.9%, the chloride ion content is 1.4-1.7ppm, and the yield is 96.5-97.4%.
2. The method for preparing triphenylphosphine rhodium carbonyl acetylacetonate according to claim 1, wherein in the second step, the fatty aldehyde is selected from one of acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde and caproaldehyde, and the mass ratio of fatty aldehyde to rhodium is 0.5-2.
3. The method for preparing triphenylphosphine carbonyl rhodium acetylacetonate according to claim 1, wherein the mass ratio of triphenylphosphine to rhodium in the second step is 2.8-3.8.
4. The method for preparing rhodium acetylacetonate triphenylphosphine carbonyl according to claim 1, wherein in the third step, the mass ratio of deionized water to acetylacetonate is 0.5.
5. The method for preparing rhodium acetylacetonate triphenylphosphine carbonyl according to claim 1, wherein in the fourth step, the vacuum drying temperature is 30 ℃ and the vacuum degree is-0.06 MPa.
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| GB2075857A (en) * | 1980-05-15 | 1981-11-25 | Davy Mckee Oil & Chem | Making hydroformylation catalysts |
| CN101172987A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Method for producing 3-(triphenylphosphine )-carbonyl hydrogenation Rh |
| CN103709205A (en) * | 2012-10-09 | 2014-04-09 | 中国石油化工股份有限公司 | Preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium, and olefin hydroformylation method |
| CN103709201A (en) * | 2012-10-09 | 2014-04-09 | 中国石油化工股份有限公司 | Preparation method of acetylacetonato dicarbonylrhodium, and olefin hydroformylation method |
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| GB2075857A (en) * | 1980-05-15 | 1981-11-25 | Davy Mckee Oil & Chem | Making hydroformylation catalysts |
| CN101172987A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Method for producing 3-(triphenylphosphine )-carbonyl hydrogenation Rh |
| CN103709205A (en) * | 2012-10-09 | 2014-04-09 | 中国石油化工股份有限公司 | Preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium, and olefin hydroformylation method |
| CN103709201A (en) * | 2012-10-09 | 2014-04-09 | 中国石油化工股份有限公司 | Preparation method of acetylacetonato dicarbonylrhodium, and olefin hydroformylation method |
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