CN114853818B - Preparation method of dicarbonyl biphosphine ligand platinum compound - Google Patents
Preparation method of dicarbonyl biphosphine ligand platinum compound Download PDFInfo
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- -1 dicarbonyl biphosphine Chemical compound 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 150000003058 platinum compounds Chemical class 0.000 title claims abstract description 31
- 239000003446 ligand Substances 0.000 title claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 71
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000003513 alkali Substances 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 24
- VURFVHCLMJOLKN-UHFFFAOYSA-N Diphosphine Natural products PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 238000001291 vacuum drying Methods 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 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 description 10
- 238000004090 dissolution Methods 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 3
- XGCDBGRZEKYHNV-UHFFFAOYSA-N 1,1-bis(diphenylphosphino)methane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 XGCDBGRZEKYHNV-UHFFFAOYSA-N 0.000 claims description 3
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 claims description 3
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 9
- 238000000921 elemental analysis Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- 229940043279 diisopropylamine Drugs 0.000 description 3
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 3
- XAFJSPPHVXDRIE-UHFFFAOYSA-L platinum(2+);triphenylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Pt+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 XAFJSPPHVXDRIE-UHFFFAOYSA-L 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- UGVHWZLAQNPMGQ-UHFFFAOYSA-L dichloroplatinum;2-diphenylphosphanylethyl(diphenyl)phosphane Chemical compound Cl[Pt]Cl.C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 UGVHWZLAQNPMGQ-UHFFFAOYSA-L 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- FBCMODDAYVHEHB-UHFFFAOYSA-N platinum;triphenylphosphane Chemical compound [Pt].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FBCMODDAYVHEHB-UHFFFAOYSA-N 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- JZUFKLXOESDKRF-UHFFFAOYSA-N Chlorothiazide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC2=C1NCNS2(=O)=O JZUFKLXOESDKRF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005937 allylation reaction Methods 0.000 description 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LWNLXVXSCCLRRZ-UHFFFAOYSA-N dichlorophosphane Chemical compound ClPCl LWNLXVXSCCLRRZ-UHFFFAOYSA-N 0.000 description 1
- QXTUMDWLAWDSEX-UHFFFAOYSA-L dichloroplatinum 3-diphenylphosphanylpropyl(diphenyl)phosphane Chemical compound Cl[Pt]Cl.C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 QXTUMDWLAWDSEX-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229960002003 hydrochlorothiazide Drugs 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 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
- C07F15/0086—Platinum compounds
- C07F15/0093—Platinum compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
-
- 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)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention belongs to the technical field of noble metal platinum catalyst synthesis, and provides a preparation method of a dicarbonyl biphosphine ligand platinum compound. The preparation method comprises the following steps: s1, dissolving a dichloro-diphosphino-platinum compound in an organic solvent to obtain a solution system A; s2, dissolving an alkali reagent in an organic solvent to obtain a solution system B; s3, dropwise adding the solution system B into the solution system A for reaction to obtain a solution system C; s4, mixing the solution system C with formaldehyde aqueous solution to carry out carbonylation reaction to obtain a dicarbonyl diphosphine ligand platinum compound; all the above steps are carried out under anaerobic conditions. The preparation method has the advantages of simple preparation process, short synthesis period and high production efficiency, greatly improves the utilization rate of the effective noble metal platinum, greatly reduces the production cost, and has obvious economic and environmental advantages.
Description
Technical Field
The invention relates to the technical field of noble metal platinum catalyst synthesis, in particular to a preparation method of a dicarbonyl biphosphine ligand platinum compound.
Background
The hydrosilation reaction is an important way for synthesizing the organosilane coupling agent and the functional organosilicon compound, and the platinum catalyst is the most effective catalyst for allylation reaction and hydrosilylation of asymmetric hydroformylation reaction, and has high reaction activity and catalytic activity. The early stage mainly adopts a chloroplatinic acid isopropanol system, but the catalyst system is unstable, has short storage period and extremely low catalytic efficiency, and the dicarbonyl biphosphine ligand platinum compound catalyst has stable storage, certain superiority and high selectivity for a specific reaction. Therefore, a preparation method of the dicarbonyl diphosphine ligand platinum compound with mild reaction conditions, high yield and high purity is developed, and the preparation method has extremely broad market prospect and great economic value.
At present, related documents are published at home and abroad on the synthesis of dicarbonyl biphosphine ligand platinum compounds, and mainly comprise the following ways:
method 1: bis (triphenylphosphine) hydrochlorofluoroplatinum is used as a platinum raw material, benzene is used as a reaction solvent, and the target product of dicarbonyl bis (triphenylphosphine) platinum is synthesized by reaction under the action of 18-crown ether-6 and potassium hydroxide, the yield is about 90%, and the reference literature is: grushin, v.v.; et al, J.Organomet.chem.,1989,371 (3), 403-419;
method 2: taking dichloro diphosphine ligand platinum compound as raw material, tetrahydrofuran as solvent, sodium borohydride, lithium aluminum hydride, sodium borohydride or hydrazine hydrochloride as reducer, reacting for more than 12 hours in carbon monoxide atmosphere to obtain target product dicarbonyl diphosphine ligand platinum compound with yield of 65-90%, reference document: a) Chatt, J.; chini, p., j.chem.soc.,1970,1538; b) Chini, p.; longoni, g., j.chem.soc.,1970,1542; c) Giannoccare, p.; sacco, a; et al, inorg.chim.acta,1979,37,455; d) Clark, h.c.; jain, V.K., coord.Chem.Rov.,1984,55,151.
In the two methods, the method 1 takes bis (triphenylphosphine) hydrochlorothiazide as a raw material, the synthesis process of the raw material is more complicated, the used organic solvent is benzene, and the organic solvent is a chemical with extremely high toxicity, and the filtrate has heavy environmental pollution and is not suitable for industrial production; the method 2 uses strong reducing agent, which can lead to severe reaction process, and toxic gas CO is used in the reaction process, which can limit the selectivity of reaction equipment, increase the equipment cost, and has the defects of long reaction time, high cost, low purity, inconvenient operation and the like, thereby greatly reducing the production efficiency and being not suitable for industrial production.
Therefore, how to provide a preparation method of a dicarbonyl biphosphine ligand platinum compound with high yield, low cost, little pollution, low energy consumption, economy, environmental protection and simple operation is a problem to be solved by the technicians in the field.
Disclosure of Invention
In view of this, the present invention provides a method for preparing a bis-carbonyl-bis-phosphine ligand platinum compound. The method aims to solve the technical problems of long reaction time, high cost, low purity, inconvenient operation and the like in the prior art.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a dicarbonyl diphosphine ligand platinum compound, which comprises the following steps:
s1, dissolving a dichloro-diphosphino-platinum compound in an organic solvent to obtain a solution system A;
s2, dissolving an alkali reagent in an organic solvent to obtain a solution system B;
s3, dropwise adding the solution system B into the solution system A for reaction to obtain a solution system C;
s4, mixing the solution system C with formaldehyde aqueous solution to carry out carbonylation reaction to obtain a dicarbonyl diphosphine ligand platinum compound;
all the above steps are carried out under anaerobic conditions.
Further, the structural formula of the dichloro-diphosphino-platinum compound is as follows:
wherein R is a biphosphinyl compound or two triphenylphosphine;
the biphosphinyl compound is one of bis (diphenylphosphino) methane, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane and 1,1' -bis (diphenylphosphino) ferrocene;
both P atoms in R are attached to Pt.
Further, in the step S1, the dissolution temperature is 50-80 ℃ and the dissolution time is 3-15 min;
the mass volume ratio of the dichloro-diphosphino-platinum compound to the organic solvent is 1g: 4-10 mL.
Further, the organic solvent 1 in the step S1 is one or more of ethanol, tetrahydrofuran, toluene, cyclohexane and 1, 4-dioxane;
the organic solvent 2 in the step S2 is methanol, ethanol or isopropanol.
Further, in the step S2, the dissolution temperature is 50-80 ℃ and the dissolution time is 3-15 min;
the alkali reagent is inorganic alkali or organic ammonia;
the inorganic base is sodium hydroxide and/or potassium hydroxide, and the organic ammonia is one or more of triethylamine, ethylenediamine and diisopropylamine;
when the alkali reagent is inorganic alkali, the mass volume ratio of the alkali reagent to the organic solvent is 1g: 3-8 mL; when the alkali reagent is organic ammonia, the mass volume ratio of the alkali reagent to the organic solvent is 1g: 0-5 mL.
Further, the reaction temperature in the step S3 is 50-80 ℃ and the reaction time is 15-60 min;
the dripping time is 1-10 min.
Further, the temperature of the carbonylation reaction in the step S4 is 50-80 ℃ and the time is 3.0-8.0 h;
the mass percentage of the formaldehyde aqueous solution is 37-40%.
Further, the molar ratio of the dichloro-bisphosphine platinum compound to the alkali agent is 1:3 to 6; the mass volume ratio of the dichloro-diphosphino-platinum compound to the formaldehyde aqueous solution is 1g: 3-5 mL.
Furthermore, the bis-carbonyl bis-phosphine ligand platinum compound obtained in the step S4 needs to be subjected to cooling, filtering, washing and vacuum drying in sequence;
the vacuum degree of the vacuum drying is less than or equal to-0.05 MPa, the temperature is 50-80 ℃ and the time is 2.0-8.0 h.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the dichlorophosphine ligand platinum compound is adopted as a platinum precursor, and under the action of an alkali reagent, a carbonylation reaction is further carried out through a formaldehyde solution, so that the reaction intensity is reduced, the environmental pollution is reduced, the required energy consumption is low, the yield of a target product is further improved to more than 96.0%, the purity is more than 98.0%, dangerous chemicals are not involved in the whole reaction process, and the operation environment is better and safer;
the preparation method has the advantages of simple preparation process, short synthesis period and high production efficiency, greatly improves the utilization rate of the effective noble metal platinum, greatly reduces the production cost, and has obvious economic and environmental advantages.
Detailed Description
The invention provides a preparation method of a dicarbonyl diphosphine ligand platinum compound, which comprises the following steps:
s1, dissolving a dichloro-diphosphino-platinum compound in an organic solvent to obtain a solution system A;
s2, dissolving an alkali reagent in an organic solvent to obtain a solution system B;
s3, dropwise adding the solution system B into the solution system A for reaction to obtain a solution system C;
s4, mixing the solution system C with formaldehyde aqueous solution to carry out carbonylation reaction to obtain a dicarbonyl diphosphine ligand platinum compound;
all the above steps are carried out under anaerobic conditions.
In the invention, the step S1 and the step S2 have no requirement of sequence.
In the invention, the structural formula of the dichloro-diphosphino-platinum compound is as follows:
wherein R is a biphosphinyl compound or two triphenylphosphine; both P atoms in R are attached to Pt.
In the present invention, the bisphosphino compound is one of bis (diphenylphosphino) methane, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane and 1,1' -bis (diphenylphosphino) ferrocene.
In the present invention, in the step S1, the dissolution temperature is 50 to 80 ℃, preferably 55 to 75 ℃, and more preferably 60 to 70 ℃; the time is 3 to 15 minutes, preferably 5 to 12 minutes, and more preferably 8 to 10 minutes;
the mass volume ratio of the dichloro-diphosphino-platinum compound to the organic solvent is 1g: 4-10 mL, preferably 1g:5 to 8mL, more preferably 1g: 6-7 mL.
In the present invention, the organic solvent 1 in the step S1 is one or more of ethanol, tetrahydrofuran, toluene, cyclohexane and 1, 4-dioxane, preferably one or more of ethanol, tetrahydrofuran and toluene, and more preferably ethanol or toluene.
In the present invention, the organic solvent 2 in the step S2 is methanol, ethanol or isopropanol, preferably methanol or ethanol, and more preferably ethanol.
In the present invention, in the step S2, the dissolution temperature is 50 to 80 ℃, preferably 55 to 75 ℃, and more preferably 60 to 70 ℃; the time is 3 to 15 minutes, preferably 5 to 12 minutes, and more preferably 8 to 10 minutes;
the alkali reagent is inorganic alkali or organic ammonia, preferably inorganic alkali;
the inorganic base is sodium hydroxide and/or potassium hydroxide, preferably sodium hydroxide; the organic ammonia is one or more of triethylamine, ethylenediamine and diisopropylamine, preferably triethylamine and/or ethylenediamine, and more preferably triethylamine;
when the alkali reagent is inorganic alkali, the mass volume ratio of the alkali reagent to the organic solvent is 1g: 3-8 mL, preferably 1g:4 to 7mL, more preferably 1g:5mL;
when the alkali reagent is organic ammonia, the mass volume ratio of the alkali reagent to the organic solvent is 1g:0 to 5mL, preferably 1g:1 to 4mL, more preferably 1g:3mL.
In the present invention, the temperature of the reaction in the step S3 is 50 to 80 ℃, preferably 55 to 75 ℃, and more preferably 60 to 70 ℃; the time is 15 to 60 minutes, preferably 20 to 50 minutes, and more preferably 30 to 40 minutes;
the time for the dropping is 1 to 10 minutes, preferably 2 to 8 minutes, and more preferably 4 to 6 minutes.
In the present invention, the time of the reaction does not include the time of the dropwise addition.
In the present invention, the carbonylation reaction temperature in the step S4 is 50 to 80 ℃, preferably 55 to 75 ℃, and more preferably 60 to 70 ℃; the time is 3.0 to 8.0 hours, preferably 4.0 to 6.0 hours, and more preferably 5.0 hours;
the mass percentage of the formaldehyde aqueous solution is 37 to 40%, preferably 38 to 39%, and more preferably 38%.
In the invention, the molar ratio of the dichloro-diphosphino-platinum compound to the alkali reagent is 1:3 to 6; preferably 1:4 to 5, more preferably 1:4, a step of; the mass volume ratio of the dichloro-diphosphino-platinum compound to the formaldehyde aqueous solution is 1g:3 to 5mL, preferably 1g:4mL.
In the invention, the dicarbonyl diphosphine ligand platinum compound obtained in the step S4 needs to be subjected to cooling, filtering, washing and vacuum drying in sequence;
the vacuum degree of the vacuum drying is less than or equal to-0.05 MPa, preferably less than or equal to-0.06 MPa, and more preferably less than or equal to-0.08 MPa; the temperature is 50 to 80 ℃, preferably 55 to 75 ℃, and more preferably 60 to 70 ℃; the time is 2.0 to 8.0 hours, preferably 3.0 to 7.0 hours, and more preferably 4.0 to 5.0 hours.
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation of the dicarbonyl diphosphine ligand platinum compound comprises the following specific preparation steps:
s1, dissolving 10.0g of dichloro bis (triphenylphosphine) platinum compound in 50mL of absolute ethyl alcohol, and stirring for 5min at 75 ℃ to obtain a solution system A;
s2, dissolving 5.2g of triethylamine in 10mL of absolute ethyl alcohol, and stirring for 5min at 75 ℃ to obtain a solution system B;
s3, dropwise adding the solution system B into the solution system A for 5min, and reacting at 75 ℃ for 20min to obtain a solution system C;
s4, mixing the solution system C with 40mL of 37% formaldehyde aqueous solution, reacting for 4 hours at 75 ℃, cooling, filtering, washing and vacuum drying after the reaction is finished to obtain 9.50g of dicarbonyl bis (triphenylphosphine) platinum compound; wherein the temperature of vacuum drying is 70 ℃, the time is 2.5 hours, and the vacuum degree is less than or equal to-0.05 MPa;
all the above steps are carried out under anaerobic conditions.
The yield of this example was 96.9% and the purity was 98.6%.
The elemental analysis results of the bis (triphenylphosphine) platinum dicarbonyl compound prepared in this example were C58.80%, H3.95% and Pt 24.80%; theoretical value is C58.83%, H3.90%, pt 25.15%.
Example 2
The preparation of the dicarbonyl diphosphine ligand platinum compound comprises the following specific preparation steps:
s1, dissolving 10.0g of dichloro bis (triphenylphosphine) platinum compound in 60ml of 1, 4-dioxane, and stirring at 55 ℃ for 10min to obtain a solution system A;
s2, dissolving 2.1g of sodium hydroxide in 15mL of methanol, and stirring for 10min at 55 ℃ to obtain a solution system B;
s3, dropwise adding the solution system B into the solution system A for 8min, and reacting at 55 ℃ for 50min to obtain a solution system C;
s4, mixing the solution system C with 45mL of 38% formaldehyde aqueous solution, reacting for 6.5h at 55 ℃, cooling, filtering, washing and vacuum drying after the reaction is finished to obtain 9.43g of dicarbonyl bis (triphenylphosphine) platinum compound; wherein the temperature of vacuum drying is 60 ℃, the time is 4.5 hours, and the vacuum degree is less than or equal to-0.05 MPa;
all the above steps are carried out under anaerobic conditions.
The yield of this example was 96.2% and the purity was 98.1%.
The elemental analysis results of the bis (triphenylphosphine) platinum dicarbonyl compound prepared in this example were C58.80%, H3.95% and Pt 24.80%; theoretical value is C58.83%, H3.90%, pt 25.15%.
Example 3
The preparation of the dicarbonyl diphosphine ligand platinum compound comprises the following specific preparation steps:
s1, dissolving 10.0g of bis (diphenylphosphino) methane platinum chloride compound in 60mL of absolute ethyl alcohol, and stirring for 10min at 70 ℃ to obtain a solution system A;
s2, dissolving 3.2g of potassium hydroxide in 20mL of absolute ethyl alcohol, and stirring for 10min at 70 ℃ to obtain a solution system B;
s3, dropwise adding the solution system B into the solution system A for 10min, and reacting at 70 ℃ for 25min to obtain a solution system C;
s4, mixing the solution system C with 50mL of 39% formaldehyde aqueous solution, reacting for 4.5 hours at 70 ℃, cooling, filtering, washing and vacuum drying after the reaction is finished to obtain 9.41g of bis (diphenylphosphino) methane dicarbonyl platinum compound; wherein the temperature of vacuum drying is 65 ℃, the time is 3.5 hours, and the vacuum degree is less than or equal to-0.05 MPa;
all the above steps are carried out under anaerobic conditions.
The yield of this example was 96.4% and the purity was 98.2%.
The elemental analysis results of the bis (diphenylphosphino) methane dicarbonyl platinum compound prepared in this example were C50.96%, H3.58%, pt 30.15%; theoretical value is C51.03%, H3.49%, pt 30.70%.
Example 4
The preparation of the dicarbonyl diphosphine ligand platinum compound comprises the following specific preparation steps:
s1, dissolving 10.0g of 1, 2-bis (diphenylphosphino) ethane platinum chloride compound in 70mL of tetrahydrofuran, and stirring at 60 ℃ for 10min to obtain a solution system A;
s2, dissolving 2.5g of sodium hydroxide in 20mL of methanol, and stirring at 60 ℃ for 10min to obtain a solution system B;
s3, dropwise adding the solution system B into the solution system A for 10min, and reacting at 60 ℃ for 45min to obtain a solution system C;
s4, mixing the solution system C with 45mL of 37% formaldehyde aqueous solution, reacting for 5.5 hours at 60 ℃, cooling, filtering, washing and vacuum drying after the reaction is finished to obtain 9.42g of 1, 2-bis (diphenylphosphino) ethane dicarbonyl platinum compound; wherein the temperature of vacuum drying is 65 ℃, the time is 3.5 hours, and the vacuum degree is less than or equal to-0.05 MPa;
all the above steps are carried out under anaerobic conditions.
The yield of this example was 96.5% and the purity was 98.2%.
Elemental analysis (for a 1, 2-bis (diphenylphosphino) ethane dicarbonyl platinum compound prepared in this example) gave C51.70%, H3.80%, pt 29.49%; theoretical value is C51.77%, H3.72%, pt 30.03%.
Example 5
The preparation of the dicarbonyl diphosphine ligand platinum compound comprises the following specific preparation steps:
s1, dissolving 10.0g of 1, 3-bis (diphenylphosphino) propane platinum chloride compound in 80mL of cyclohexane, and stirring for 5min at 70 ℃ to obtain a solution system A;
s2, dissolving 6.0g of diisopropylamine in 10mL of absolute ethyl alcohol, and stirring at 70 ℃ for 5min to obtain a solution system B;
s3, dropwise adding the solution system B into the solution system A for 7min, and reacting at 70 ℃ for 35min to obtain a solution system C;
s4, mixing the solution system C with 40mL of 40% formaldehyde aqueous solution, reacting for 4.5 hours at 70 ℃, cooling, filtering, washing and vacuum drying after the reaction is finished to obtain 9.42g of 1, 3-bis (diphenylphosphino) propane dicarbonyl platinum compound; wherein the temperature of vacuum drying is 75 ℃, the time is 3.0h, and the vacuum degree is less than or equal to-0.05 MPa;
all the above steps are carried out under anaerobic conditions.
The yield of this example was 96.4% and the purity was 98.3%.
The elemental analysis results of the 1, 3-bis (diphenylphosphino) propane dicarbonyl platinum compound prepared in this example were C52.41%, H4.01%, pt 28.90%; theoretical value is C52.49%, H3.95%, pt 29.40%.
Example 6
The preparation of the dicarbonyl diphosphine ligand platinum compound comprises the following specific preparation steps:
s1, dissolving 10.0g of 1, 4-bis (diphenylphosphino) butane platinum chloride compound in 90mL of toluene, and stirring at 80 ℃ for 5min to obtain a solution system A;
s2, dropwise adding 5.8g of triethylamine into the solution system A for 2min, and reacting at 80 ℃ for 20min to obtain a solution system C;
s4, mixing the solution system C with 35mL of 38% formaldehyde aqueous solution, reacting for 3.5h at 80 ℃, cooling, filtering, washing and vacuum drying after the reaction is finished to obtain 9.45g of 1, 4-bis (diphenylphosphino) butane dicarbonyl platinum compound; wherein the temperature of vacuum drying is 80 ℃, the time is 2.0h, and the vacuum degree is less than or equal to-0.05 MPa;
all the above steps are carried out under anaerobic conditions.
The yield of this example was 96.7% and the purity was 98.5%.
The elemental analysis results of the 1, 4-bis (diphenylphosphino) butane dicarbonyl platinum compound prepared in this example were C53.13%, H4.21%, pt 28.36%; theoretical value is C53.17%, H4.16%, pt 28.79%.
Example 7
The preparation of the dicarbonyl diphosphine ligand platinum compound comprises the following specific preparation steps:
s1, dissolving 10.0g of 1,1' -bis (diphenylphosphine) ferrocene platinum chloride compound in a mixed solution of 40mL of absolute ethyl alcohol and 40mL of tetrahydrofuran, and stirring for 5min at 65 ℃ to obtain a solution system A;
s2, dissolving 3.7g of ethylenediamine in 5mL of isopropanol, and stirring for 5min at 65 ℃ to obtain a solution system B;
s3, dropwise adding the solution system B into the solution system A for 4min, and reacting at 65 ℃ for 40min to obtain a solution system C;
s4, mixing the solution system C with 30mL of 39% formaldehyde aqueous solution, reacting for 5.0h at 65 ℃, cooling, filtering, washing and vacuum drying after the reaction is finished to obtain 9.45g of 1,1' -bis (diphenylphosphine) ferrocene dicarbonyl platinum compound; wherein the temperature of vacuum drying is 75 ℃, the time is 2.5 hours, and the vacuum degree is less than or equal to-0.05 MPa;
all the above steps are carried out under anaerobic conditions.
The yield of this example was 96.4% and the purity was 98.4%.
The elemental analysis results of the 1,1' -bis (diphenylphosphine) ferrocene dicarbonyl platinum compound prepared in this example were C53.61%, H3.57%, pt 23.83%; theoretical value is C53.67%, H3.50%, pt 24.22%.
Example 8
The preparation of the dicarbonyl diphosphine ligand platinum compound comprises the following specific preparation steps:
s1, dissolving 1.0kg of 1, 2-bis (diphenylphosphino) ethane platinum chloride compound in 6.0L of absolute ethyl alcohol, and stirring for 10min at 70 ℃ to obtain a solution system A;
s2, dissolving 620.0g of triethylamine in 500mL of absolute ethyl alcohol, and stirring for 10min at 70 ℃ to obtain a solution system B;
s3, dropwise adding the solution system B into the solution system A for 10min, and reacting at 70 ℃ for 30min to obtain a solution system C;
s4, mixing the solution system C with 4.0L of 40% formaldehyde aqueous solution, reacting for 5.0h at 70 ℃, cooling, filtering, washing and vacuum drying after the reaction is finished to obtain 945.99g of 1, 2-bis (diphenylphosphino) ethane dicarbonyl platinum compound; wherein the temperature of vacuum drying is 70 ℃, the time is 3.5 hours, and the vacuum degree is less than or equal to-0.05 MPa;
all the above steps are carried out under anaerobic conditions.
The yield of this example was 96.9% and the purity was 98.5%.
Elemental analysis (for the 1, 2-bis (diphenylphosphino) ethane dicarbonyl platinum compound prepared in this example) gave C51.73%, H3.78%, pt 29.58%; theoretical value is C51.77%, H3.72%, pt 30.03%.
Comparative example 1
This comparative example was conducted in the same manner as in example 1 except that no anaerobic condition was set, and 7.85g of a bis (triphenylphosphine) platinum compound was obtained, which was obtained in a yield of 80.1% and a purity of 96.2%. Therefore, the reaction process is under the aerobic condition, the reduction process of the formaldehyde solution can be inhibited, or by-products are generated in the reaction process, so that the yield and purity of the target product are reduced.
Comparative example 2
This comparative example was conducted in the same manner as in example 1 except that no alkali agent was added, 4.42g of a bis (triphenylphosphine) platinum compound was obtained, and the yield of this comparative example was 45.1% and the purity was 98.2%. Thus, the reaction is carried out under the condition of no alkali reagent, and Cl on the raw material dichloro bis (triphenylphosphine) platinum compound - Difficult to break off, and the carbonyl can not coordinate, so that the yield of the target product is obviously lower.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. A method for preparing a dicarbonyl diphosphine ligand platinum compound, which is characterized by comprising the following steps:
s1, dissolving a dichloro-diphosphino-platinum compound in an organic solvent 1 to obtain a solution system A;
s2, dissolving an alkali reagent in the organic solvent 2 to obtain a solution system B;
s3, dropwise adding the solution system B into the solution system A for reaction to obtain a solution system C;
s4, mixing the solution system C with formaldehyde aqueous solution to carry out carbonylation reaction to obtain a dicarbonyl diphosphine ligand platinum compound;
all the steps are carried out under the anaerobic condition;
the structural formula of the dichloro-diphosphino-platinum compound is as follows:
wherein R is a biphosphinyl compound or two triphenylphosphine;
the biphosphinyl compound is one of bis (diphenylphosphino) methane, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane and 1,1' -bis (diphenylphosphino) ferrocene;
two P atoms in R are connected with Pt;
the mass volume ratio of the dichloro-diphosphino-platinum compound to the organic solvent is 1g: 4-10 mL;
the alkali reagent is triethylamine, and the mass volume ratio of the alkali reagent to the organic solvent is 1g: 0-5 mL;
in the step S3, the reaction temperature is 50-80 ℃ and the reaction time is 15-60 min; the dripping time is 1-10 min;
in the step S4, the temperature of the carbonylation reaction is 50-80 ℃ and the time is 3.0-8.0 h; the mass percentage of the formaldehyde aqueous solution is 37-40%;
the molar ratio of the dichloro-diphosphino-platinum compound to the alkali agent is 1:3 to 6; the mass volume ratio of the dichloro-diphosphino-platinum compound to the formaldehyde aqueous solution is 1g: 3-5 mL.
2. The method according to claim 1, wherein the dissolution temperature in the step S1 is 50 to 80 ℃ for 3 to 15min.
3. The preparation method according to claim 2, wherein the organic solvent 1 in the step S1 is one or more of ethanol, tetrahydrofuran, toluene, cyclohexane and 1, 4-dioxane;
the organic solvent 2 in the step S2 is methanol, ethanol or isopropanol.
4. A process according to any one of claims 1 to 3, wherein in step S2, the dissolution temperature is 50 to 80 ℃ and the time is 3 to 15min.
5. The preparation method according to claim 4, wherein the bis-carbonyl-bis-phosphine ligand platinum compound obtained in step S4 is subjected to cooling, filtering, washing and vacuum drying in sequence;
the vacuum degree of the vacuum drying is less than or equal to-0.05 MPa, the temperature is 50-80 ℃ and the time is 2.0-8.0 h.
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| CN109071578A (en) * | 2016-05-06 | 2018-12-21 | 巴斯夫欧洲公司 | P- chiral phosphine ligand and its purposes for asymmetric syntheses |
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| CN112300217A (en) * | 2020-11-25 | 2021-02-02 | 江苏开放大学（江苏城市职业学院） | Preparation method of Cis-ruthenium-salen azacyclo-carbene |
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| CN102186863A (en) * | 2008-11-05 | 2011-09-14 | 科莱恩金融(Bvi)有限公司 | Method for producing mono-hydroxyfunctionalized dialkylphosphinic acids and esters and salts thereof by means of acroleins and use thereof |
| CN109071578A (en) * | 2016-05-06 | 2018-12-21 | 巴斯夫欧洲公司 | P- chiral phosphine ligand and its purposes for asymmetric syntheses |
| CN110483582A (en) * | 2019-09-11 | 2019-11-22 | 陕西师范大学 | Azepine Cabbeen palladium complex crystal and its synthetic method and preparing the application in amide compound |
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