CN112321437A - Preparation method of tetra-n-propyl high ammonium ruthenate - Google Patents
Preparation method of tetra-n-propyl high ammonium ruthenate Download PDFInfo
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- CN112321437A CN112321437A CN202011293859.8A CN202011293859A CN112321437A CN 112321437 A CN112321437 A CN 112321437A CN 202011293859 A CN202011293859 A CN 202011293859A CN 112321437 A CN112321437 A CN 112321437A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title claims description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000004537 pulping Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000605 extraction Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 9
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims abstract description 9
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000012065 filter cake Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical group CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001335 aliphatic alkanes Chemical group 0.000 claims abstract description 5
- 239000003208 petroleum Substances 0.000 claims abstract description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003446 ligand Substances 0.000 abstract description 2
- 238000011112 process operation Methods 0.000 abstract description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of tetra-n-propyl ammonium homoruthenate, which comprises the following steps: (1) mixing anhydrous sodium carbonate, sodium bromate and water, stirring uniformly, and stirring for 1-2h at 20-40 ℃; (2) adding ruthenium chloride hydrate into the reaction system in the step (1), and reacting for 5-10h at the temperature of 20-40 ℃; (3) dropwise adding 25wt% of tetrapropylammonium hydroxide into the reaction system in the step (2), and reacting for 5-10h at 20-30 ℃ after dropwise adding; (4) adding an extraction liquid into the reaction system for extraction, concentrating under normal pressure until no liquid is discharged, adjusting the temperature to be 20-30 ℃, then adding a pulping solvent, pulping, filtering, and drying a filter cake in vacuum; wherein the extract is dichloroethane or chloroform; the pulping solvent is alkane or petroleum ether. The method provided by the invention has the advantages of mild reaction conditions, simple and convenient process operation, small ligand usage amount and high comprehensive yield, the purity of the prepared tetrapropylammonium hydroxide is more than or equal to 99%, the yield is more than or equal to 99%, and the high-efficiency utilization of the technology is realized.
Description
Technical Field
The invention belongs to the technical field of precious metal catalyst preparation, and particularly relates to a preparation method of tetra-n-propyl high ammonium ruthenate.
Background
Tetra-n-propyl ammonium ruthenate is a mild metal oxidation catalyst used under neutral conditions, and compared with PCC and an oxidation reagent Swern, the tetra-n-propyl ammonium ruthenate can completely cover the functions of the PCC and the oxidation reagent Swern in the reaction process of catalyzing and oxidizing alcohol to aldehyde and ketone, and better results can be obtained. In a very complex system, tetra-n-propyl homoruthenium ammonium also shows excellent performance when the oxidation reaction of different types of alcohols is completed. The catalyst has wide application in the aspects of complex medicines, liquid crystal materials, functional materials, compounds with biological activity and the like.
If the method for preparing the high-efficiency tetra-n-propyl ammonium homoruthenate can be provided, the method has great significance.
Disclosure of Invention
The invention provides a preparation method of tetra-n-propyl ammonium ruthenate, which is used for reaction under mild reaction conditions, and is simple to operate, and the purity of the prepared tetra-n-propyl ammonium ruthenate is more than or equal to 99%.
A preparation method of tetra-n-propyl ammonium homoruthenate comprises the following steps:
(1) mixing anhydrous sodium carbonate, sodium bromate and water, stirring uniformly, and stirring for 1-2h at 20-40 ℃;
(2) adding ruthenium chloride hydrate into the reaction system in the step (1), and reacting for 5-10h at the temperature of 20-40 ℃;
(3) dropwise adding 25wt% of tetrapropylammonium hydroxide into the reaction system in the step (2), and reacting for 5-10h at 20-30 ℃ after dropwise adding;
(4) adding an extraction liquid into the reaction system for extraction, concentrating under normal pressure until no liquid is discharged, adjusting the temperature to be 20-30 ℃, then adding a pulping solvent, pulping, filtering, and drying a filter cake in vacuum; wherein the extract is dichloroethane or chloroform; the pulping solvent is alkane or petroleum ether.
Preferably, the alkane is n-hexane, cyclohexane or n-heptane.
Preferably, the mass ratio of the anhydrous sodium carbonate, the sodium bromate, the water, the 25% tetrapropylammonium hydroxide, the extract, the pulping solvent and the ruthenium chloride hydrate is (10-15): (30-50): (150-200): (3-3.5): (50-60): (3-5): 1.
preferably, the vacuum drying conditions are as follows: drying at 30 deg.C under 0.06-0.08MPa for 2-6 hr.
Preferably, the vacuum drying conditions are as follows: the temperature of the extraction was 45 ℃.
The invention has the advantages that:
1. the method provided by the invention has the advantages of mild reaction conditions, simple and convenient process operation, small ligand usage amount and high comprehensive yield;
2. the purity of the tetrapropylammonium hydroxide prepared by the method is more than or equal to 99 percent, the yield is more than or equal to 99 percent, and the high-efficiency utilization of the technology is realized.
Detailed Description
Example 1
A preparation method of tetra-n-propyl ammonium homoruthenate comprises the following steps:
(1) 20g of anhydrous sodium carbonate, 60g of sodium bromate and 300g of water are mixed and stirred uniformly, and stirred for 2 hours at the temperature of 30 ℃;
(2) adding 2g of ruthenium chloride hydrate into the reaction system in the step (1), and reacting for 10 hours at 40 ℃;
(3) dropwise adding 6g of 25wt% tetrapropylammonium hydroxide into the reaction system in the step (2), and reacting for 7h at 30 ℃ after dropwise adding;
(4) adding 100g of extract dichloroethane into the reaction system, extracting at 45 ℃, concentrating under normal pressure until no liquid is discharged, adjusting the temperature to 20 ℃, adding 6g of pulping solvent n-heptane, pulping, filtering, and vacuum-drying the filter cake at 30 ℃ and 0.06-0.08MPa for 6 h.
2.523g of tetra-n-propyl ammonium homoruthenate is prepared in this example with a yield of 99.4% and a purity of 99.3%. Theoretical element analysis results: 41.01 percent of C, 8.03 percent of H, 18.21 percent of O, 3.99 percent of N and 28.76 percent of Ru; actual elemental analysis results: 40.99% of C, 8.05% of H, 18.23% of O, 3.92% of N and 28.81% of Ru.
Example 2
A preparation method of tetra-n-propyl ammonium homoruthenate comprises the following steps:
(1) mixing 25g of anhydrous sodium carbonate, 80g of sodium bromate and 350g of water, stirring uniformly, and stirring at 40 ℃ for 1 h;
(2) adding 2g of ruthenium chloride hydrate into the reaction system in the step (1), and reacting for 5h at the temperature of 30 ℃;
(3) dropwise adding 6.5g of 25wt% tetrapropylammonium hydroxide into the reaction system in the step (2), and reacting for 5 hours at 30 ℃ after dropwise adding;
(4) adding 110g of extract dichloroethane into the reaction system, extracting at 45 ℃, concentrating under normal pressure until no liquid is discharged, adjusting the temperature to 20 ℃, then adding 8g of pulping solvent n-hexane, pulping, filtering, and drying the filter cake at 30 ℃ and 0.06-0.08MPa in vacuum for 4 h.
2.531 g of ammonium tetra-n-propyl homoruthenate are prepared in this example in a yield of 99.7% and a purity of 99.6%. Theoretical element analysis results: 41.01 percent of C, 8.03 percent of H, 18.21 percent of O, 3.99 percent of N and 28.76 percent of Ru; actual elemental analysis results: 41.02 percent of C, 8.02 percent of H, 18.24 percent of O, 3.95 percent of N and 28.77 percent of Ru.
Example 3
A preparation method of tetra-n-propyl ammonium homoruthenate comprises the following steps:
(1) mixing 30g of anhydrous sodium carbonate, 100g of sodium bromate and 400g of water, stirring uniformly, and stirring for 1h at the temperature of 30 ℃;
(2) adding 2g of ruthenium chloride hydrate into the reaction system in the step (1), and reacting for 7h at 20 ℃;
(3) 7g of 25wt% tetrapropylammonium hydroxide is dropwise added into the reaction system in the step (2), and after the dropwise addition is finished, the reaction is carried out for 10 hours at the temperature of 20 ℃;
(4) adding 120g of extraction liquid chloroform into the reaction system, extracting at 45 ℃, concentrating under normal pressure until no liquid is discharged, adjusting the temperature to 20 ℃, then adding 8g of petroleum ether serving as a pulping solvent, pulping, filtering, and drying a filter cake for 2 hours under vacuum at 30 ℃ and 0.06-0.08 MPa.
2.520g of ammonium tetra-n-propyl homoruthenate were prepared in 99.3% yield and 99.2% purity. Theoretical element analysis results: 41.01 percent of C, 8.03 percent of H, 18.21 percent of O, 3.99 percent of N and 28.76 percent of Ru; actual elemental analysis results: 41.04 percent of C, 8.05 percent of H, 18.17 percent of O, 3.94 percent of N and 28.80 percent of Ru.
Example 4
A preparation method of tetra-n-propyl ammonium homoruthenate comprises the following steps:
(1) mixing 28g of anhydrous sodium carbonate, 90g of sodium bromate and 380g of water, stirring uniformly, and stirring for 2 hours at the temperature of 20 ℃;
(2) adding 2g of ruthenium chloride hydrate into the reaction system in the step (1), and reacting for 7h at 35 ℃;
(3) 7g of 25wt% tetrapropylammonium hydroxide is dropwise added into the reaction system in the step (2), and after the dropwise addition is finished, the reaction is carried out for 8 hours at 25 ℃;
(4) adding 120g of extraction liquid chloroform into the reaction system, extracting at 45 ℃, concentrating under normal pressure until no liquid is discharged, adjusting the temperature to 30 ℃, then adding 10g of pulping solvent cyclohexane, pulping, filtering, and drying the filter cake at 20 ℃ under 0.06-0.08MPa for 6 hours in vacuum to obtain the product.
2.526g of tetra-n-propyl ammonium homoruthenate were prepared in 99.5% yield and 99.7% purity in this example. Theoretical element analysis results: 41.01 percent of C, 8.03 percent of H, 18.21 percent of O, 3.99 percent of N and 28.76 percent of Ru; actual elemental analysis results: 41.03 percent of C, 8.05 percent of H, 18.18 percent of O, 3.95 percent of N and 28.79 percent of Ru.
Claims (5)
1. A preparation method of tetra-n-propyl ammonium homoruthenate is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing anhydrous sodium carbonate, sodium bromate and water, stirring uniformly, and stirring for 1-2h at 20-40 ℃;
(2) adding ruthenium chloride hydrate into the reaction system in the step (1), and reacting for 5-10h at the temperature of 20-40 ℃;
(3) dropwise adding 25wt% of tetrapropylammonium hydroxide into the reaction system in the step (2), and reacting for 5-10h at 20-30 ℃ after dropwise adding;
(4) adding an extraction liquid into the reaction system for extraction, concentrating under normal pressure until no liquid is discharged, adjusting the temperature to be 20-30 ℃, then adding a pulping solvent, pulping, filtering, and drying a filter cake in vacuum; wherein the extract is dichloroethane or chloroform; the pulping solvent is alkane or petroleum ether.
2. The method according to claim 1, wherein said ammonium tetra-n-propylhomoruthenate is prepared by: the alkane is n-hexane, cyclohexane or n-heptane.
3. The method according to claim 2, wherein said ammonium tetra-n-propylhomoruthenate is prepared by: the mass ratio of the anhydrous sodium carbonate, the sodium bromate, the water, the 25% tetrapropylammonium hydroxide, the extract, the pulping solvent and the ruthenium chloride hydrate is (10-15): (30-50): (150-200): (3-3.5): (50-60): (3-5): 1.
4. the method according to claim 3, wherein said ammonium tetra-n-propylhomoruthenate is prepared by: the vacuum drying conditions are as follows: drying at 20-40 deg.C under 0.06-0.08MPa for 2-6 hr.
5. The method according to claim 1, wherein said ammonium tetra-n-propylhomoruthenate is prepared by: the vacuum drying conditions are as follows: the temperature of the extraction was 45 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028535A (en) * | 2022-06-28 | 2022-09-09 | 浙江微通催化新材料有限公司 | Preparation method of tetrapropyl high ammonium ruthenate |
| CN115028536A (en) * | 2022-06-27 | 2022-09-09 | 昆明贵金属研究所 | Preparation method of tetra-n-propyl ammonium perruthenate (VII) |
Citations (2)
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| US20010041803A1 (en) * | 2000-03-21 | 2001-11-15 | Kasitu Gertrude C. | Conversion of 9-dihydro-13-acetylbaccatin III to baccatin III and 10-deacetyl baccatin III |
| US20170222138A1 (en) * | 2014-10-31 | 2017-08-03 | Fujifilm Corporation | Ruthenium removal composition and method of producing magnetoresistive random access memory |
-
2020
- 2020-11-18 CN CN202011293859.8A patent/CN112321437A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010041803A1 (en) * | 2000-03-21 | 2001-11-15 | Kasitu Gertrude C. | Conversion of 9-dihydro-13-acetylbaccatin III to baccatin III and 10-deacetyl baccatin III |
| US20170222138A1 (en) * | 2014-10-31 | 2017-08-03 | Fujifilm Corporation | Ruthenium removal composition and method of producing magnetoresistive random access memory |
Non-Patent Citations (6)
| Title |
|---|
| ABDEL-GHANY F. SHOAIR: "A novel method for preparing of oxoruthenates complexes:trans-[RuO3(OH)2]2-,[RuO4]-,(n-Pr4N)+[RuO4]- and [RuO4] and their use as catalytic oxidants", 《BULL. KOREAN CHEM. SOC.》 * |
| ANDREA-KATHARINA C. SCHMIDT等: "Tetrapropylammonium perruthenate catalyzed glycol cleavage to carboxylic (Di)acids", 《ORG.LETT.》 * |
| ANDREA-KATHARINA C. SCHMIDT等: "TPAP-catalyzed direct oxidation of primary alcohols to carboxylic acids through stabilized aldehyde hydrates", 《ORG.LETT.》 * |
| TIMOTHY J. ZERK等: "Elucidating the mechanism of the Ley-Griffith(TPAP)alcohol oxidation", 《CHEM.SCI.》 * |
| VICTORIA FARMER等: "The oxidation of alcohols in substituted imidazolium ionic liquids using ruthenium catalysts", 《GREEN CHEMISTRY》 * |
| VICTORIA FARMER等: "The oxidation of alcohols using ruthenium catalysts and imidazolium ionic liquids", 《PROCEEDING OF THE ELECTROCHEMICAL SOCIETY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028536A (en) * | 2022-06-27 | 2022-09-09 | 昆明贵金属研究所 | Preparation method of tetra-n-propyl ammonium perruthenate (VII) |
| CN115028535A (en) * | 2022-06-28 | 2022-09-09 | 浙江微通催化新材料有限公司 | Preparation method of tetrapropyl high ammonium ruthenate |
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Application publication date: 20210205 |