CN110078771B - Preparation method of iridium catalyst - Google Patents
Preparation method of iridium catalyst Download PDFInfo
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- CN110078771B CN110078771B CN201910490325.5A CN201910490325A CN110078771B CN 110078771 B CN110078771 B CN 110078771B CN 201910490325 A CN201910490325 A CN 201910490325A CN 110078771 B CN110078771 B CN 110078771B
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 34
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 238000006722 reduction reaction Methods 0.000 claims abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000460 chlorine Substances 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 13
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 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 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 7
- 238000001704 evaporation Methods 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 5
- 230000008020 evaporation Effects 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- UFJSITOHZAUZBO-UHFFFAOYSA-K cycloocta-1,3-diene;trichloroiridium Chemical compound Cl[Ir](Cl)Cl.C1CCC=CC=CC1 UFJSITOHZAUZBO-UHFFFAOYSA-K 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- ORBBTCHHNMWMCP-UHFFFAOYSA-K cycloocta-1,5-diene trichloroiridium Chemical class [Ir](Cl)(Cl)Cl.C1=CCCC=CCC1 ORBBTCHHNMWMCP-UHFFFAOYSA-K 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- DNZZPKYSGRTNGK-PQZOIKATSA-N (1z,4z)-cycloocta-1,4-diene Chemical compound C1C\C=C/C\C=C/C1 DNZZPKYSGRTNGK-PQZOIKATSA-N 0.000 description 1
- HITROERJXNWVOI-SOFGYWHQSA-N (5e)-octa-1,5-diene Chemical compound CC\C=C\CCC=C HITROERJXNWVOI-SOFGYWHQSA-N 0.000 description 1
- WVQBLGZPHOPPFO-LBPRGKRZSA-N (S)-metolachlor Chemical compound CCC1=CC=CC(C)=C1N([C@@H](C)COC)C(=O)CCl WVQBLGZPHOPPFO-LBPRGKRZSA-N 0.000 description 1
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- 239000005617 S-Metolachlor Substances 0.000 description 1
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- -1 chloroiridate Chemical compound 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CALMYRPSSNRCFD-UHFFFAOYSA-J tetrachloroiridium Chemical compound Cl[Ir](Cl)(Cl)Cl CALMYRPSSNRCFD-UHFFFAOYSA-J 0.000 description 1
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Classifications
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- 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
- C07F15/0033—Iridium compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an iridium catalyst [ IrCl (C)8H12)]2The preparation method comprises the following steps: dissolving a compound containing iridium and chlorine in water in an oxygen-free environment to prepare an iridium solution; adding cyclooctadiene into the iridium solution, slowly dropwise adding a reducing agent, and carrying out reduction reaction until no precipitate is generated; the solution was filtered, the solid was washed with water and then crystallized by evaporation to give [ IrCl (C)8H12)]2. The method has the advantages of short reaction time, high product purity and high yield.
Description
Technical Field
The invention relates to the technical field of organic chemistry, in particular to the field of noble metal homogeneous catalyst synthesis, and especially relates to [ IrCl (C)8H12)]2The preparation method of (1).
Background
[IrCl(C8H12)]2As a noble metal homogeneous catalyst and a precursor of various iridium catalysts, the iridium catalyst has wide application in the chemical industry field. In particular in the industrial production of the herbicide s-metolachlor, [ IrCl (C)8H12)]2Is a catalyst precursor for asymmetric hydrogenation reaction which is important in the synthesis process.
Herde, J, L (organic synttheses, 1974,15,18) originally reported the synthesis of 1, 5-cyclooctadiene iridium chloride dimer by reacting iridium chloride with ethanol under oxygen-free reflux conditions for over 24 hours.
JP2006045089A discloses a method for producing cyclooctadiene iridium chloride, in which the molar amount of 1, 5-octadiene is 7 to 9 times the molar amount of iridium chloride, and the purity of the resulting 1, 5-cyclooctadiene iridium chloride dimer is low, and in order to remove 1, 3-cyclooctadiene and 1, 4-cyclooctadiene as impurities, a large amount of water is added at the end of the reaction, and then the product is precipitated, which method cannot produce a product having high purity.
US639980482 discloses a preparation method of 1, 5-cyclooctadiene iridium chloride, wherein the reaction process is that iridium trichloride or iridium tetrachloride and alcohol (the number of carbon atoms is 3-9) are refluxed for a period of time, in the preparation method, when the number of the carbon atoms of the alcohol is larger than that of the alcohol, the alcohol and water in the reaction are difficult to be mutually dissolved, a large amount of alcohol is added (the volume ratio of the alcohol to the water is 2: 1-1: 1, the significance is lost, and the problem of post-treatment is brought, the purity and the activity of the cyclooctadiene iridium chloride obtained by the preparation method are poor.
The existing reaction has the disadvantages of low product purity, large raw material consumption, incapability of recycling, high production cost and environmentally-friendly process due to long reaction time.
Therefore, it is required to develop [ IrCl (C) ]8H12)]2Short reaction time, high product purity and high yield [ IrCl (C)8H12)]2The preparation method of (1).
Disclosure of Invention
The invention aims to solve the problem of the prior [ IrCl (C) ]8H12)]2The preparation method generally has the problems of low product purity, large raw material consumption, incapability of recycling, high production cost and environmental-friendliness due to long reaction time.
In order to solve the technical problems, the technical scheme of the invention is a preparation method of an iridium catalyst, which comprises the following steps of preparing the iridium catalyst from [ IrCl (C)8H12)]2；
S1, dissolving a compound containing iridium and chlorine in water in an oxygen-free environment to prepare an iridium solution;
s2, adding cyclooctadiene into the iridium solution, and uniformly stirring;
s3, slowly adding a reducing agent dropwise to perform a reduction reaction until no precipitate is generated;
s4, filtering the solution obtained in S3, washing the solid with water, and then carrying out evaporative crystallization to obtain [ IrCl (C)8H12)]2。
In step S1, the iridium and chlorine containing compound is selected from at least one of iridium chloride, chloroiridate, ammonium chloroiridate, and sodium chloroiridate. The concentration of the iridium solution is preferably 8% to 30%.
In step S2, the molar ratio of iridium to cyclooctadiene added was 1: 2.
In step S3, the reducing agent is at least one selected from hydrazine hydrate and hydroboron aqueous solution. The temperature of the reduction reaction is 50-100 ℃, and preferably, the reduction temperature is 80-90 ℃. And the reducing agent was added dropwise with vigorous stirring.
In step S4, the cyclooctadiene is used continuously after the filtrate is subjected to liquid separation.
The water in the above steps is oxygen-free water.
The method of the invention has short reaction time, [ IrCl (C)8H12)]2The product has high purity and yield. The purity of the iridium complex obtained by the method is 99%, the iridium content is more than or equal to 56.7%, and the carbon content in elemental analysis is 28.32-28.90%.
Drawings
FIG. 1 is a nuclear magnetic H-NMR chart of iridium cyclooctadienechloride prepared in comparative example 1.
FIG. 2 is a nuclear magnetic H-NMR chart of cyclooctadiene iridium chloride obtained in example 1.
FIG. 3 is a nuclear magnetic H-NMR chart of the iridium cyclooctadienechloride obtained in example 2.
FIG. 4 is a nuclear magnetic H-NMR chart of cyclooctadiene iridium chloride obtained in example 3.
FIG. 5 is a nuclear magnetic H-NMR chart of cyclooctadiene iridium chloride obtained in example 4.
Detailed Description
For the sake of understanding, the present invention will be described in detail below by way of specific examples. It is to be expressly understood that the description is illustrative only and is not intended as a definition of the limits of the invention. Many variations and modifications of the present invention will be apparent to those skilled in the art in light of the teachings of this specification.
Example 1
Dissolving iridium chloride in oxygen-free water to obtain 10% iridium solution, adding cyclooctadiene with 2 times of molar ratio, dropwise adding hydrazine hydrate under oxygen-free condition and vigorous stirring, reacting at 90 deg.C until no precipitate is generated, filtering, washing filter cake with oxygen-free water, evaporating and crystallizing to obtain iridium chloride [ IrCl (C)8H12)]2. And separating the filtrate, and continuing using the cyclooctadiene. The yield is 99.5%, the mass purity is 99%, and the iridium content: 56.71%, elemental analysis carbon content: 28.35%, nuclear magnetismH-NMR is shown in figure 2.
Example 2
Dissolving chloroiridic acid in oxygen-free water to obtain 10% iridium solution, adding cyclooctadiene with 2 times of molar ratio, dropwise adding sodium borohydride under oxygen-free condition and vigorous stirring at 80 deg.C until no precipitate is generated, filtering, washing filter cake with oxygen-free water, evaporating and crystallizing to obtain iridium chloride [ IrCl (C)8H12)]2. And separating the filtrate, and continuing using the cyclooctadiene. The yield is 99.5%, the mass purity is 99%, and the iridium content: 56.77%, elemental analysis carbon content: 28.38%, nuclear magnetic H-NMR as shown in FIG. 3.
Example 3
Dissolving sodium chloroiridate in oxygen-free water to obtain 10% iridium solution, adding cyclooctadiene with 2 times of molar ratio, dropwise adding hydrazine hydrate under oxygen-free condition and vigorous stirring at reaction temperature of 90 deg.C, filtering, washing filter cake with oxygen-free water, evaporating and crystallizing to obtain iridium chloride [ IrCl (C)8H12)]2. And separating the filtrate, and continuing using the cyclooctadiene. The yield is 99.5%, the mass purity is 99%, and the iridium content: 56.66%, elemental analysis carbon content: 28.32%, nuclear magnetic H-NMR as shown in FIG. 4.
Example 4
Dissolving iridium chloride in oxygen-free water to obtain a solution with the iridium content of 10%, adding cyclooctadiene with the molar ratio of 2 times, dropwise adding a sodium borohydride solution under the oxygen-free condition and vigorous stirring, reacting at the temperature of 80 ℃, dropwise adding until no precipitate is generated, filtering, washing a filter cake with oxygen-free water, and evaporating and crystallizing to obtain the iridium chloride [ IrCl (C)8H12)]2. And separating the filtrate, and continuing using the cyclooctadiene. The yield is 99.5%, the mass purity is 99%, and the iridium content: 56.83%, elemental analysis carbon content: 28.41%, and NMR as shown in figure 5.
Comparative example 1
[IrCl(C8H12)]2Ethanol process
Dissolving iridium chloride in a mixed solution of oxygen-free water and industrial alcohol, adding cyclooctadiene with the molar ratio of 2 times, and stirring and refluxing for more than 24 hours under the oxygen-free condition. Cooled to room temperature and the precipitated solid was filtered, washed with cold methanol and dried. Yield 70%, mass purity 98%, iridium content: 56.08%, elemental analysis carbon content: 28.04% and nuclear magnetic H-NMR as shown in figure 1.
The above examples are only for illustrating the technical idea and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. A preparation method of an iridium catalyst comprises the following steps: s1, dissolving a compound containing iridium and chlorine in water in an oxygen-free environment to prepare an iridium solution;
s2, adding cyclooctadiene into the iridium solution, and uniformly stirring;
s3, slowly adding a reducing agent dropwise to perform a reduction reaction until no precipitate is generated;
s4, filtering the solution obtained in S3, washing the solid with water, and then carrying out evaporative crystallization to obtain [ IrCl (C)8H12)]2；
In step S3, the reducing agent is at least one selected from hydrazine hydrate and aqueous solution of borohydride.
2. The production method according to claim 1, wherein in step S1, the iridium and chlorine containing compound is selected from at least one of iridium chloride, chloroiridic acid, ammonium chloroiridate, and sodium chloroiridate.
3. The method according to claim 1, wherein the concentration of the iridium solution in step S1 is preferably 8-30%.
4. The method according to claim 1, wherein in step S2, the molar ratio of iridium to cyclooctadiene added is 1: 2.
5. The method according to claim 1, wherein the temperature of the reduction reaction in step S3 is 50 to 100 ℃.
6. The method according to claim 1, wherein the reducing agent is added dropwise with vigorous stirring in step S3.
7. The method according to claim 1, wherein in step S4, the cyclooctadiene is used after the filtrate is separated.
8. The method of claim 1, wherein the water used in the above step is oxygen-free water.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230999A (en) * | 2014-08-20 | 2014-12-24 | 昆明贵金属研究所 | Method for preparing dicarbonyl iridium acetylacetonate (I) |
| CN104926884A (en) * | 2015-04-23 | 2015-09-23 | 金川集团股份有限公司 | Preparation method of dichloro(1,5-cyclooctadiene) platinum (II) |
| CN105585596A (en) * | 2015-12-04 | 2016-05-18 | 江西省汉氏贵金属有限公司 | Preparation method of rhodium compounds |
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| CN106380490A (en) * | 2016-09-09 | 2017-02-08 | 昆明理工大学 | One-step synthesis method of (1,5-cyclooctadiene)-dichloro iridium dipolymer |
| CN106496279A (en) * | 2016-09-09 | 2017-03-15 | 昆明理工大学 | The synthetic method of (1,5 cyclo-octadiene) two chloro palladium |
| CN106632496A (en) * | 2016-11-29 | 2017-05-10 | 金川集团股份有限公司 | Preparation method of (1,5-cyclooctadiene) rhodium chloride (I) dimers |
-
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- 2019-06-06 CN CN201910490325.5A patent/CN110078771B/en active Active
Patent Citations (7)
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|---|---|---|---|---|
| CN104230999A (en) * | 2014-08-20 | 2014-12-24 | 昆明贵金属研究所 | Method for preparing dicarbonyl iridium acetylacetonate (I) |
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| CN105585596A (en) * | 2015-12-04 | 2016-05-18 | 江西省汉氏贵金属有限公司 | Preparation method of rhodium compounds |
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