CN106674285B - A method of preparing acetylacetonatodicarrhodium rhodium - Google Patents
A method of preparing acetylacetonatodicarrhodium rhodium Download PDFInfo
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- CN106674285B CN106674285B CN201611023730.9A CN201611023730A CN106674285B CN 106674285 B CN106674285 B CN 106674285B CN 201611023730 A CN201611023730 A CN 201611023730A CN 106674285 B CN106674285 B CN 106674285B
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- rhodium
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- 239000010948 rhodium Substances 0.000 title claims abstract description 56
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 55
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 83
- 239000000243 solution Substances 0.000 claims abstract description 78
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 67
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 57
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims abstract description 13
- -1 2,4-pentanedione sodium salt Chemical class 0.000 claims abstract description 11
- 235000019441 ethanol Nutrition 0.000 claims abstract description 11
- 238000001291 vacuum drying Methods 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 17
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims 3
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract 2
- 239000002994 raw material Substances 0.000 description 6
- 150000003283 rhodium Chemical class 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 5
- HSSMNYDDDSNUKH-UHFFFAOYSA-K trichlororhodium;hydrate Chemical compound O.Cl[Rh](Cl)Cl HSSMNYDDDSNUKH-UHFFFAOYSA-K 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 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 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000005406 washing 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of methods for preparing acetylacetonatodicarrhodium rhodium to mix this method comprises: (1) prepares the aqueous solution of certain density rhodium chloride with toluene, is reacted after then passing to CO gas heating；(2) acetylacetone,2,4-pentanedione sodium salt is added into solution, the reaction was continued；(3) a certain amount of triphenylphosphine, heating reaction are added into reaction solution；(4) reaction solution filters, and is successively washed with deionized water, ethyl alcohol and n-hexane, and vacuum drying obtains acetylacetonatodicarrhodium rhodium product.Preparation method of the invention has the features such as rhodium conversion per pass is high, simple process, mild condition, product impurity content is few.
Description
Technical field:
The present invention relates to Organometallic Chemistry fields, it is desirable to provide a kind of more efficient by soluble rhodium salt " one kettle way "
The method for preparing acetylacetonatodicarrhodium rhodium.
Background technique:
Acetylacetonatodicarrhodium rhodium (Rh (acac) (PPh3) (CO)) it is usually used in the preparation of catalyzed alkene hydroformylation
The catalyst of aldehyde reaction is widely used in the industry of hydroformylation of propene producing butyladehyde since its catalytic activity is high, selectivity is good
In device.
The method of the disclosed synthesis acetylacetonatodicarrhodium rhodium of most of prior art is generally divided into two steps: first
Be rhodium trichloride hydrate in n,N-Dimethylformamide solvent with DMF provide carbonyl reacted, then again with addition
The reaction of acetylacetone,2,4-pentanedione rhodium carbonyl generates rhodium dicarbonyl acetylacetonate (Rh (acac) (CO)2), product settled, be filtered, washed and
Rhodium dicarbonyl acetylacetonate intermediate is obtained after drying and other steps；Second step is after rhodium dicarbonyl acetylacetonate is dissolved in organic solvent
It is reacted again with a certain amount of triphenylphosphine and generates acetylacetonatodicarrhodium rhodium, then through sedimentation, filtering and drying and other steps
Obtain acetylacetonatodicarrhodium rhodium product.
Two-step method synthesizes the initial total recovery of acetylacetonatodicarrhodium rhodium only 70% or so, although then passing through
Total recovery is increased to 90% or more by changing deposition condition, improving the condition optimizings such as solvent, still by the effort of researcher
Entire technical process is still needed by two-step reaction, and repeatedly processes, the whole process steps such as precipitating filtering, dry do not have substantially
It is reduced, the rhodium loss in last handling process cannot be ignored.
Chinese patent CN104169290A discloses a kind of " one-pot synthesis method " and prepares acetylacetonatodicarrhodium rhodium
Method, reacted in the solution as carbonyl source with rhodium using carbon monoxide, then again addition sodium bicarbonate effect under with
Acetylacetone,2,4-pentanedione reaction, adds triphenylphosphine into reaction solution, filtration washing obtains acetylacetone,2,4-pentanedione triphenylphosphine after the reaction was completed
Rhodium carbonyl.Rhodium dicarbonyl acetylacetonate intermediate is not required to be separated in this method, is directly reacted with triphenylphosphine in reaction solution,
But initial reaction stage needs to be passed through CO gas for a long time, utilization rate of carbon monoxide is low；And containing a certain amount of in product
Chlorine impurity, to influence the catalytic activity of product.
Summary of the invention:
The present invention aiming at the problems existing in the prior art, provides a kind of more efficient acetylacetone,2,4-pentanedione triphenylphosphine carbonyl
Rhodium preparation method has the features such as rhodium conversion per pass is high, simple process, mild condition, product impurity content is few.
The present invention provides a kind of method for preparing acetylacetonatodicarrhodium rhodium, this method " one kettle way " is by rhodium salt
Convert acetylacetonatodicarrhodium rhodium.It is realized especially by following scheme:
A kind of method for preparing acetylacetonatodicarrhodium rhodium of the present invention, includes the following steps:
(a) aqueous solution for configuring certain density rhodium chloride, is then added toluene, the rhodium of the rhodium solution into solution
Concentration is 1%-30%, and the volumetric usage of the toluene is calculated as 5-50mL/g with rhodium chloride quality；
(b) reaction solution is heated to 50-80 DEG C, then passes to carbon monoxide, guarantee that reaction vessel is closed to keep certain
Pressure, stirring keeps for 3-8 hour, and the pressure of the reactor is 0-0.02MPa (gauge pressure)；
(c) reaction solution is cooled to room temperature, after release, acetylacetone,2,4-pentanedione sodium salt is added into solution, is stirred to react, the levulinic
The molar ratio of rhodium in ketone sodium salt additional amount and reaction solution is 3:1-9:1；
(d) triphenylphosphine is added into reaction solution, be heated to 50-120 DEG C reaction, the triphenylphosphine additional amount with react
The molar ratio of rhodium in liquid is 1-1.1；
(e) after reaction solution is cooling, filtering, filter cake is successively washed with deionized water, ethyl alcohol and n-hexane, and vacuum drying obtains
Acetylacetonatodicarrhodium rhodium product.
Using carbon monoxide as carbonyl source, and reacts and carried out under the conditions of closed container micro-positive pressure, carbon monoxide
Utilization rate is high, substantially without carbon monoxide emission in reaction process.Using acetylacetone,2,4-pentanedione sodium salt as raw material, which was both played
The effect of acetylacetone,2,4-pentanedione (acac) radical sources is provided, and plays the role of alkali, the acidity of rhodium salt hydrolysis formation can be neutralized
It is acted on chloride ion and generates sodium chloride.Using toluene and water two-phase solvent as reaction dissolvent, the effect of reaction, extraction is played,
After rhodium salt is reacted with carbon monoxide and acetylacetone,2,4-pentanedione sodium in aqueous solution, become oleophilic substance and enter toluene phase, thus and water
Unreacted rhodium salt and sodium chloride separation in phase, avoid the entrainment for having chlorine impurity in final product.
In the method for the present invention, following steps are preferably included:
(a) aqueous solution for configuring the rhodium chloride of 1%-30%, is then added toluene, the volume of the toluene into solution
Dosage is calculated as 10-30mL/g with rhodium chloride quality；
(b) reaction solution is heated to 60-70 DEG C, then passes to carbon monoxide, guarantee that reaction vessel is closed to keep certain
Pressure, stirring keeps for 3-8 hour, and the pressure of the reactor is 0-0.01MPa (gauge pressure)；
(c) reaction solution is cooled to room temperature, after release, acetylacetone,2,4-pentanedione sodium salt is added into solution, is stirred to react, the levulinic
The molar ratio of rhodium in ketone sodium salt additional amount and reaction solution is 3:1-5:1；
(d) triphenylphosphine is added into reaction solution, be heated to 50-120 DEG C reaction, the triphenylphosphine additional amount with react
The molar ratio of rhodium in liquid is 1-1.05；
(e) after reaction solution is cooling, filtering, filter cake is successively washed with deionized water, ethyl alcohol and n-hexane, and vacuum drying obtains
Acetylacetonatodicarrhodium rhodium product.
More preferably include the following steps:
(a) aqueous solution for configuring certain density rhodium chloride, is then added toluene, the rhodium of the rhodium solution into solution
Concentration is 10%-15%, and the volumetric usage of the toluene is calculated as 10-15mL/g with rhodium chloride quality；
(b) reaction solution is heated to 60-70 DEG C, then passes to carbon monoxide, guarantee that reaction vessel is closed to keep certain
Pressure, stirring keeps for 3-8 hour, and the pressure of the reactor is 0-0.01MPa (gauge pressure)；
(c) reaction solution is cooled to room temperature, after release, acetylacetone,2,4-pentanedione sodium salt is added into solution, is stirred to react, the levulinic
The molar ratio of rhodium in ketone sodium salt additional amount and reaction solution is 3:1-4:1；
(d) triphenylphosphine is added into reaction solution, be heated to 50-120 DEG C reaction, the triphenylphosphine additional amount with react
The molar ratio of rhodium in liquid is 1-1.02；
(e) after reaction solution is cooling, filtering, filter cake is successively washed with deionized water, ethyl alcohol and n-hexane, and vacuum drying obtains
Acetylacetonatodicarrhodium rhodium product.
The method of the present invention the utility model has the advantages that the present invention with water-soluble rhodium salt raw material, intermediate product be not required to it is to be separated, one
Acetylacetonatodicarrhodium rhodium is prepared in a reactor, reaction process utilization rate of carbon monoxide is high, discharge amount of exhaust gas
Few, product yield is high, and chlorinity is low.
Specific embodiment
The present invention further illustrates preparation method by following embodiments, but does not constitute the limit to the scope of the present invention
System.
Embodiment 1
10g rhodium trichloride hydrate is dissolved in 56g deionized water, 90mL toluene is then added into solution, by reaction solution
65 DEG C are heated to, carbon monoxide is then passed to, guarantees that reaction vessel is closed to keep certain pressure 0.05MPa (gauge pressure), stirs
It mixes, is kept for 5 hours.Reaction solution is cooled to room temperature, after release, mono- water acetylacetone,2,4-pentanedione sodium of 18.7g is added into solution, is stirred to react 3
Hour；Then 10.3g triphenylphosphine solid is added into reaction solution, is heated to 80 DEG C of reactions；It after reaction solution is cooling, filters, filter
Cake is successively washed with deionized water, ethyl alcohol and n-hexane, and vacuum drying obtains acetylacetonatodicarrhodium rhodium production at 45 DEG C
Product.It is 98.5% by benchmark calculated yield of the rhodium in raw material, the chlorinity in acetylacetonatodicarrhodium rhodium is through detecting
0.0022% (chlorine ion electrode method).
Embodiment 2
10g rhodium trichloride hydrate is dissolved in 30g deionized water, 150mL toluene is then added into solution, by reaction solution
60 DEG C are heated to, carbon monoxide is then passed to, guarantees that reaction vessel is closed to keep certain pressure 0.03MPa (gauge pressure), stirs
It mixes, is kept for 6 hours.Reaction solution is cooled to room temperature, after release, mono- water acetylacetone,2,4-pentanedione sodium of 14.2g is added into solution, is stirred to react 5
Hour；Then 10.2g triphenylphosphine solid is added into reaction solution, is heated to 85 DEG C of reactions；It after reaction solution is cooling, filters, filter
Cake is successively washed with deionized water, ethyl alcohol and n-hexane, and vacuum drying obtains acetylacetonatodicarrhodium rhodium production at 45 DEG C
Product.It is 97.6% by benchmark calculated yield of the rhodium in raw material, the chlorinity in acetylacetonatodicarrhodium rhodium is through detecting
0.0019% (chlorine ion electrode method).
Embodiment 3
10g rhodium trichloride hydrate is dissolved in 36g deionized water, 50mL toluene is then added into solution, by reaction solution
65 DEG C are heated to, carbon monoxide is then passed to, guarantees that reaction vessel is closed to keep certain pressure 0.05MPa (gauge pressure), stirs
It mixes, is kept for 5 hours.Reaction solution is cooled to room temperature, after release, mono- water acetylacetone,2,4-pentanedione sodium of 18.0g is added into solution, is stirred to react 3
Hour；Then 10.5g triphenylphosphine solid is added into reaction solution, is heated to 95 DEG C of reactions；It after reaction solution is cooling, filters, filter
Cake is successively washed with deionized water, ethyl alcohol and n-hexane, and vacuum drying obtains acetylacetonatodicarrhodium rhodium production at 45 DEG C
Product.It is 98.7% by benchmark calculated yield of the rhodium in raw material, the chlorinity in acetylacetonatodicarrhodium rhodium is through detecting
0.0023% (chlorine ion electrode method).
Embodiment 4
10g rhodium trichloride hydrate is dissolved in 20g deionized water, 100mL toluene is then added into solution, by reaction solution
70 DEG C are heated to, carbon monoxide is then passed to, guarantees that reaction vessel is closed to keep certain pressure 0.01MPa (gauge pressure), stirs
It mixes, is kept for 8 hours.Reaction solution is cooled to room temperature, after release, mono- water acetylacetone,2,4-pentanedione sodium of 40.0g is added into solution, is stirred to react 3
Hour；Then 11.0g triphenylphosphine solid is added into reaction solution, is heated to 85 DEG C of reactions；It after reaction solution is cooling, filters, filter
Cake is successively washed with deionized water, ethyl alcohol and n-hexane, and vacuum drying obtains acetylacetonatodicarrhodium rhodium production at 45 DEG C
Product.It is 98.1% by benchmark calculated yield of the rhodium in raw material, the chlorinity in acetylacetonatodicarrhodium rhodium is through detecting
0.0025% (chlorine ion electrode method).
Claims (3)
1. a kind of method for preparing acetylacetonatodicarrhodium rhodium, it is characterised in that it the following steps are included:
(a) aqueous solution for configuring the rhodium chloride of 1wt%-30wt%, is then added toluene into solution, and the volume of the toluene is used
Amount is calculated as 5-50mL/g with rhodium chloride quality；
(b) reaction solution is heated to 50-80 DEG C, then passes to carbon monoxide, guarantee that reaction vessel is closed to keep 0-0.02MPa
Pressure, stirring, keep 3-8 hours；
(c) reaction solution is cooled to room temperature, after release, acetylacetone,2,4-pentanedione sodium salt is added into solution, is stirred to react, the acetylacetone,2,4-pentanedione sodium
The molar ratio of rhodium in salt additional amount and reaction solution is 3:1-9:1；
(d) triphenylphosphine is added into reaction solution, is heated to 50-120 DEG C and reacts, in the triphenylphosphine additional amount and reaction solution
Rhodium molar ratio be 1-1.1；
(e) after reaction solution is cooling, filtering, filter cake is successively washed with deionized water, ethyl alcohol and n-hexane, and vacuum drying obtains acetyl
Acetone triphenylphosphine rhodium carbonyl product.
2. according to the method for claim 1, it is characterised in that it the following steps are included:
(a) aqueous solution for configuring the rhodium chloride of 1%-30%, is then added toluene into solution, the volumetric usage of the toluene with
Rhodium chloride quality is calculated as 10-30mL/g；
(b) reaction solution is heated to 60-70 DEG C, then passes to carbon monoxide, guarantee that reaction vessel is closed to keep certain pressure
Power, stirring are kept for 3-8 hours, and the pressure of the reactor is 0-0.01MPa；
(c) reaction solution is cooled to room temperature, after release, acetylacetone,2,4-pentanedione sodium salt is added into solution, is stirred to react, the acetylacetone,2,4-pentanedione sodium
The molar ratio of rhodium in salt additional amount and reaction solution is 3:1-5:1；
(d) triphenylphosphine is added into reaction solution, is heated to 50-120 DEG C and reacts, in the triphenylphosphine additional amount and reaction solution
Rhodium molar ratio be 1-1.05；
(e) after reaction solution is cooling, filtering, filter cake is successively washed with deionized water, ethyl alcohol and n-hexane, and vacuum drying obtains acetyl
Acetone triphenylphosphine rhodium carbonyl product.
3. according to the method for claim 1, which comprises the following steps:
(a) aqueous solution for configuring certain density rhodium chloride, is then added toluene, the rhodium concentration of the rhodium solution into solution
Volumetric usage for 10%-15%, the toluene is calculated as 10-15mL/g with rhodium chloride quality；
(b) reaction solution is heated to 60-70 DEG C, then passes to carbon monoxide, guarantee that reaction vessel is closed to keep certain pressure
Power, stirring are kept for 3-8 hours, and the pressure of the reactor is 0-0.01MPa；
(c) reaction solution is cooled to room temperature, after release, acetylacetone,2,4-pentanedione sodium salt is added into solution, is stirred to react, the acetylacetone,2,4-pentanedione sodium
The molar ratio of rhodium in salt additional amount and reaction solution is 3:1-4:1；
(d) triphenylphosphine is added into reaction solution, is heated to 50-120 DEG C and reacts, in the triphenylphosphine additional amount and reaction solution
Rhodium molar ratio be 1-1.02；
(e) after reaction solution is cooling, filtering, filter cake is successively washed with deionized water, ethyl alcohol and n-hexane, and vacuum drying obtains acetyl
Acetone triphenylphosphine rhodium carbonyl product.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104169290A (en) * | 2012-04-25 | 2014-11-26 | 优美科股份公司及两合公司 | Process for preparing diketonato-rhodium(i)-carbonyl complexes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104169290A (en) * | 2012-04-25 | 2014-11-26 | 优美科股份公司及两合公司 | Process for preparing diketonato-rhodium(i)-carbonyl complexes |
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| Title |
|---|
| 高效水-有机两相催化研究进展;毛卉等;《四川师范大学学报(自然科学版)》;20130331;第36卷(第2期);第306-311页 |
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