CN111087274A - Method for preparing bis (norbornadiene) rhodium tetrafluoroborate - Google Patents
Method for preparing bis (norbornadiene) rhodium tetrafluoroborate Download PDFInfo
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- CN111087274A CN111087274A CN201911292165.XA CN201911292165A CN111087274A CN 111087274 A CN111087274 A CN 111087274A CN 201911292165 A CN201911292165 A CN 201911292165A CN 111087274 A CN111087274 A CN 111087274A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/38—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of dienes or alkynes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
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Abstract
The invention belongs to the technical field of precious metal preparation, and relates to a method for preparing bis (norbornadiene) rhodium tetrafluoroborate, which takes rhodium trichloride hydrate and (norbornadiene) as raw materials, and obtains red bis (norbornadiene) rhodium tetrafluoroborate solid through exchange reaction with silver tetrafluoroborate ions and filter pressing under the protection of inert gas.
Description
Technical Field
The invention belongs to the technical field of precious metal preparation, relates to synthesis of a rhodium complex, and particularly relates to a method for preparing bis (norbornadiene) rhodium tetrafluoroborate.
Background
Metal rhodium complexes have wide application in both metalorganic chemistry and organic synthetic chemistry. Rhodium bis (norbornadiene) tetrafluoroborate is not only a raw material for synthesizing a plurality of complex metal rhodium complexes, but also is often used together with other ligands to catalyze a plurality of reactions such as coupling, hydrogenation, addition and the like.
The bis (norbornadiene) rhodium tetrafluoroborate has unstable physical and chemical properties and is easy to react with oxygen, and the existing preparation method has the disadvantages of complex process, low yield, high preparation cost and difficult popularization and application.
Disclosure of Invention
Aiming at the problems of the prior art, the invention provides a method for preparing bis (norbornadiene) rhodium tetrafluoroborate, which has the advantages of simple process, easy operation and low production cost, and improves the product yield and purity of the bis (norbornadiene) rhodium tetrafluoroborate.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for preparing rhodium bis (norbornadiene) tetrafluoroborate, which is characterized by comprising the following steps: the method comprises the following steps:
(1) putting rhodium trichloride hydrate and norbornadiene into an organic solvent, heating and refluxing, concentrating and filtering to obtain a norbornadiene rhodium chloride dimer;
(2) dissolving the norbornadiene rhodium chloride dimer obtained in the step (1) in an organic solvent under the protection of inert gas, adding silver tetrafluoroborate, and carrying out ion exchange reaction to obtain a bis (norbornadiene) rhodium tetrafluoroborate solution;
(3) and (3) under the protection of inert gas, adding tetrahydrofuran into the bis (norbornadiene) rhodium tetrafluoroborate solution in the step (2), performing filter pressing by using a sand plate filter tube, concentrating and cooling the mother liquor obtained by the filter pressing, performing filter pressing by using the sand plate filter tube again, and circulating the steps to obtain red bis (norbornadiene) rhodium tetrafluoroborate solid.
Preferably, the mass ratio of the rhodium trichloride hydrate to the norbornadiene is 1 (3.0-6.0).
Preferably, the organic solvent of step (1) is any one of methanol, ethanol, isopropanol or n-butanol.
Preferably, the reflux temperature in the step (1) is 75-85 ℃, and the reflux time is 1-3 h.
Preferably, the mass ratio of the norbornadiene rhodium chloride dimer to the silver tetrafluoroborate in the step (2) is 1 (2.5-3.5).
Preferably, the organic solvent in the step (2) is any one of dichloromethane, 1, 2-dichloroethane or chloroform.
Preferably, the ion exchange reaction time in the step (2) is 10-18 h.
Preferably, the ratio of the adding amount of the tetrahydrofuran in the step (3) to the volume of the reaction liquid is 1 (1.0-1.5).
Preferably, the inert gas is any one of nitrogen or argon.
The organic solvent is subjected to pre-deoxidation treatment according to the prior art, such as an ultrasonic gas exchange method, a purging method, a freezing and air-extracting method and the like.
The invention has the beneficial effects that:
(1) the invention provides a method for preparing bis (norbornadiene) rhodium tetrafluoroborate, which takes rhodium trichloride hydrate and norbornadiene as raw materials, and obtains red bis (norbornadiene) rhodium tetrafluoroborate solid through exchange reaction with silver tetrafluoroborate ions and filter pressing under the protection of inert gas;
(2) the invention provides a method for preparing bis (norbornadiene) rhodium tetrafluoroborate, which improves the yield and the purity of a bis (norbornadiene) rhodium tetrafluoroborate product by improving a preparation process, so that the solid purity of the bis (norbornadiene) rhodium tetrafluoroborate reaches more than 99 percent, and the yield reaches more than 92 percent.
Detailed Description
Example 1
A process for preparing rhodium bis (norbornadiene) tetrafluoroborate comprising the steps of:
(1) taking rhodium trichloride hydrate and norbornadiene according to the mass ratio of 1:3.0, placing the rhodium trichloride hydrate and the norbornadiene into a methanol solvent which is subjected to deoxidation treatment in advance, heating and refluxing at the reflux temperature of 75 ℃ for 3 hours, and then concentrating and filtering to obtain a norbornadiene rhodium chloride dimer;
(2) under the environment of nitrogen protection, dissolving the norbornadiene rhodium chloride dimer obtained in the step (1) in a dichloromethane solvent subjected to deoxidation treatment in advance, adding silver tetrafluoroborate, and carrying out ion exchange reaction for 10 hours to obtain a bis (norbornadiene) rhodium tetrafluoroborate solution;
wherein the mass ratio of norbornadiene rhodium chloride dimer to silver tetrafluoroborate is 1: 2.5;
(3) under the protection of nitrogen, adding tetrahydrofuran into the bis (norbornadiene) rhodium tetrafluoroborate solution in the step (2) according to the volume ratio of 1:1, performing filter pressing by using a sand plate filter tube, concentrating and cooling mother liquor obtained by the filter pressing, performing filter pressing again by using the sand plate filter tube, and circulating the steps to obtain 12.9g of red bis (norbornadiene) rhodium tetrafluoroborate solid, wherein the yield is 93.1%, the content of the measured metal rhodium is 27.25%, and the theoretical content of the metal rhodium is 27.52%.
Example 2
A process for preparing rhodium bis (norbornadiene) tetrafluoroborate comprising the steps of:
(1) taking rhodium trichloride hydrate and norbornadiene according to the mass ratio of 1:6.0, placing the rhodium trichloride hydrate and the norbornadiene into an ethanol solvent which is subjected to deoxidation treatment in advance, heating and refluxing at the reflux temperature of 85 ℃ for 1h, and then concentrating and filtering to obtain a norbornadiene rhodium chloride dimer;
(2) under the protection of argon, dissolving the norbornadiene rhodium chloride dimer obtained in the step (1) into a 1, 2-dichloroethane solvent subjected to deoxidation treatment in advance, adding silver tetrafluoroborate, and carrying out ion exchange reaction for 18 hours to obtain a bis (norbornadiene) rhodium tetrafluoroborate solution;
wherein the mass ratio of norbornadiene rhodium chloride dimer to silver tetrafluoroborate is 1: 3.0;
(3) under the protection of argon, adding tetrahydrofuran into the bis (norbornadiene) rhodium tetrafluoroborate solution in the step (2) according to the volume ratio of 1:1.3, performing filter pressing by using a sand plate filter tube, concentrating and cooling mother liquor obtained by the filter pressing, performing filter pressing again by using the sand plate filter tube, and circulating the steps to obtain 13.0 red bis (norbornadiene) rhodium tetrafluoroborate solid, wherein the yield is 93.5%, the content of the measured metal rhodium is 27.34%, and the content of the theoretical metal rhodium is 27.52%.
Example 3
A process for preparing rhodium bis (norbornadiene) tetrafluoroborate comprising the steps of:
(1) taking rhodium trichloride hydrate and norbornadiene according to the mass ratio of 1:5.0, placing the rhodium trichloride hydrate and the norbornadiene into an ethanol solvent which is subjected to deoxidation treatment in advance, heating and refluxing at the reflux temperature of 80 ℃ for 2 hours, and then concentrating and filtering to obtain a norbornadiene rhodium chloride dimer;
(2) under the protection of argon, dissolving the norbornadiene rhodium chloride dimer obtained in the step (1) in a chloroform solvent subjected to pre-deoxidation treatment, adding silver tetrafluoroborate, and carrying out ion exchange reaction for 15 hours to obtain a bis (norbornadiene) rhodium tetrafluoroborate solution;
wherein the mass ratio of norbornadiene rhodium chloride dimer to silver tetrafluoroborate is 1: 3.5;
(3) under the protection of argon, adding tetrahydrofuran into the bis (norbornadiene) rhodium tetrafluoroborate solution in the step (2) according to a volume ratio of 1:1.5, performing filter pressing by using a sand plate filter tube, concentrating and cooling mother liquor obtained by the filter pressing, performing filter pressing again by using the sand plate filter tube, and circulating the steps to obtain 12.9g of red bis (norbornadiene) rhodium tetrafluoroborate solid, wherein the yield is 93.8%, the content of the measured metal rhodium is 27.29%, and the content of the theoretical metal rhodium is 27.52%.
Example 4
A process for preparing rhodium bis (norbornadiene) tetrafluoroborate comprising the steps of:
(1) taking rhodium trichloride hydrate and norbornadiene according to the mass ratio of 1:4.0, placing the rhodium trichloride hydrate and the norbornadiene into an ethanol solvent which is subjected to deoxidation treatment in advance, heating and refluxing at the reflux temperature of 85 ℃ for 2.5 hours, concentrating and filtering to obtain a norbornadiene rhodium chloride dimer;
(2) under the environment of nitrogen protection, dissolving the norbornadiene rhodium chloride dimer obtained in the step (1) in a dichloromethane solvent subjected to pre-deoxidation treatment, adding silver tetrafluoroborate, and carrying out ion exchange reaction for 13 hours to obtain a bis (norbornadiene) rhodium tetrafluoroborate solution;
wherein the mass ratio of norbornadiene rhodium chloride dimer to silver tetrafluoroborate is 1: 3.0;
(3) under the protection of argon, adding tetrahydrofuran into the bis (norbornadiene) rhodium tetrafluoroborate solution obtained in the step (2) according to the volume ratio of 1:1, performing filter pressing by using a sand plate filter tube, concentrating and cooling mother liquor obtained by the filter pressing, performing filter pressing again by using the sand plate filter tube, and circulating the steps to obtain 13.1g of red bis (norbornadiene) rhodium tetrafluoroborate solid, wherein the yield is 92%, the content of the measured metal rhodium is 27.31%, and the content of the theoretical metal rhodium is 27.52%.
Claims (9)
1. A method for preparing rhodium bis (norbornadiene) tetrafluoroborate, which is characterized by comprising the following steps: the method comprises the following steps:
(1) putting rhodium trichloride hydrate and norbornadiene into an organic solvent, heating and refluxing, concentrating and filtering to obtain a norbornadiene rhodium chloride dimer;
(2) dissolving the norbornadiene rhodium chloride dimer obtained in the step (1) in an organic solvent under the protection of inert gas, adding silver tetrafluoroborate, and carrying out ion exchange reaction to obtain a bis (norbornadiene) rhodium tetrafluoroborate solution;
(3) and (3) under the protection of inert gas, adding tetrahydrofuran into the bis (norbornadiene) rhodium tetrafluoroborate solution in the step (2), performing filter pressing by using a sand plate filter tube, concentrating and cooling the mother liquor obtained by the filter pressing, performing filter pressing by using the sand plate filter tube again, and circulating the steps to obtain red bis (norbornadiene) rhodium tetrafluoroborate solid.
2. The process for preparing rhodium bis (norbornadiene) tetrafluoroborate according to claim 1, wherein: the mass ratio of the rhodium trichloride hydrate to the norbornadiene is 1 (3.0-6.0).
3. The process for preparing rhodium bis (norbornadiene) tetrafluoroborate according to claim 2, wherein: the organic solvent in the step (1) is any one of methanol, ethanol, isopropanol or n-butanol.
4. The process for preparing rhodium bis (norbornadiene) tetrafluoroborate according to claim 3, wherein: the reflux temperature in the step (1) is 75-85 ℃, and the reflux time is 1-3 h.
5. The process for preparing rhodium bis (norbornadiene) tetrafluoroborate according to claim 1, wherein: the mass ratio of the norbornadiene rhodium chloride dimer and the silver tetrafluoroborate in the step (2) is 1 (2.5-3.5).
6. The process of claim 5 for the preparation of rhodium bis (norbornadiene) tetrafluoroborate, wherein: the organic solvent in the step (2) is any one of dichloromethane, 1, 2-dichloroethane or chloroform.
7. The process for preparing rhodium bis (norbornadiene) tetrafluoroborate according to claim 6, wherein: the ion exchange reaction time in the step (2) is 10-18 h.
8. The process for preparing rhodium bis (norbornadiene) tetrafluoroborate according to claim 1, wherein: the ratio of the addition amount of tetrahydrofuran to the volume of the reaction solution in the step (3) is 1 (1.0-1.5).
9. The process for preparing rhodium bis (norbornadiene) tetrafluoroborate according to claim 1, wherein: the inert gas is any one of nitrogen or argon.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113955765A (en) * | 2021-12-22 | 2022-01-21 | 苏州欣诺科生物科技有限公司 | Preparation method of silver tetrafluoroborate |
| CN113980057A (en) * | 2021-10-26 | 2022-01-28 | 昆明贵金属研究所 | One-pot method for preparing bis (dienylrhodium) (I) nitrate [ RhL [)2]NO3Method of synthesis of |
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2019
- 2019-12-16 CN CN201911292165.XA patent/CN111087274B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| PATRICIA MARCE等: "Synthesis of D- and L-Carbocyclic Nucleosides via Rhodium Catalyzed Asymmetric Hydroacylation as the Key Step", 《ORGANIC LETTERS》 * |
| PETER ANDREAS BOEG等: "Real-Time Detection of Intermediates in Rhodium-Catalyzed Hydrogenation of Alkynes and Alkenes by Dissolution DNP", 《JOURNAL OF PHYSICAL CHEMISTRY C》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113980057A (en) * | 2021-10-26 | 2022-01-28 | 昆明贵金属研究所 | One-pot method for preparing bis (dienylrhodium) (I) nitrate [ RhL [)2]NO3Method of synthesis of |
| CN113980057B (en) * | 2021-10-26 | 2023-10-03 | 昆明贵金属研究所 | One-pot method for preparing diene rhodium (I) nitrate [ RhL ] 2 ]NO 3 Is synthesized by the method of (2) |
| CN113955765A (en) * | 2021-12-22 | 2022-01-21 | 苏州欣诺科生物科技有限公司 | Preparation method of silver tetrafluoroborate |
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