CN112592372A - Preparation method of bis (cyanobenzene) palladium dichloride - Google Patents
Preparation method of bis (cyanobenzene) palladium dichloride Download PDFInfo
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- CN112592372A CN112592372A CN202011506479.8A CN202011506479A CN112592372A CN 112592372 A CN112592372 A CN 112592372A CN 202011506479 A CN202011506479 A CN 202011506479A CN 112592372 A CN112592372 A CN 112592372A
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- Prior art keywords
- palladium
- bis
- cyanophenyl
- filtering
- palladium dichloride
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- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 title abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 91
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 37
- WXNOJTUTEXAZLD-UHFFFAOYSA-L benzonitrile;dichloropalladium Chemical compound Cl[Pd]Cl.N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 WXNOJTUTEXAZLD-UHFFFAOYSA-L 0.000 claims abstract description 32
- 238000001914 filtration Methods 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 239000000706 filtrate Substances 0.000 claims abstract description 20
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000012065 filter cake Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 26
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 238000001514 detection method Methods 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000000543 intermediate Substances 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
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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 System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
Abstract
The invention discloses a preparation method of bis (cyanophenyl) palladium dichloride, which comprises the following steps: (1) dissolving palladium powder in aqua regia to prepare a palladium active group, and mixing the palladium active group with benzonitrile after cooling; (2) distilling to remove water, heating for reaction, and filtering; (3) and cooling the filtrate, adding the cooled filtrate into an organic solvent, separating out a solid, filtering, washing the obtained filter cake with the organic solvent, and drying in vacuum. The method provided by the invention uses palladium powder as a raw material to replace palladium chloride in the prior art, so that the reaction cost is reduced, and the prepared product has high purity and high yield.
Description
Technical Field
The invention belongs to the technical field of precious metal catalyst preparation, and particularly relates to a preparation method of bis (cyanophenyl) palladium dichloride.
Background
The bis (cyanophenyl) palladium dichloride is an important metal palladium catalyst, is widely applied to various organic chemical reactions such as addition, coupling and the like, and is an important catalyst for synthesizing medical intermediates, liquid crystal materials, functional materials and the like. Meanwhile, the bis (cyanobenzene) palladium dichloride is also a precursor for preparing various complex homogeneous catalysts and has wide application in the field of homogeneous catalysis.
However, in the synthesis of such catalysts disclosed in the prior art, palladium chloride is used as a raw material for preparation, and the production cost is high. Therefore, the preparation method of the bis (cyanophenyl) palladium dichloride with low cost is significant.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the preparation method of the bis (cyanophenyl) palladium dichloride, palladium powder is used for replacing palladium chloride in the prior art, the bis (cyanophenyl) palladium dichloride can be prepared through one-step reaction, and the production cost is reduced.
A preparation method of bis (cyanophenyl) palladium dichloride comprises the following steps:
(1) dissolving palladium powder in aqua regia to prepare a palladium active group, and mixing the palladium active group with benzonitrile after cooling;
(2) distilling to remove water, heating for reaction, and filtering;
(3) and cooling the filtrate, adding the cooled filtrate into an organic solvent, separating out a solid, filtering, washing the obtained filter cake with the organic solvent, and drying in vacuum.
Preferably, the organic solvent is any one of n-hexane, petroleum ether, n-heptane and n-pentane.
Preferably, the ratio of the palladium powder, the aqua regia, the benzonitrile and the organic solvent is as follows: 1 g: (2-4) mL: (3-8) mL: (5-10) mL.
Preferably, the heating reaction in step (2) is carried out at 130-150 ℃ for 3-5 h.
Preferably, the conditions for preparing the palladium active set in step (1) are as follows: dissolving palladium powder in aqua regia, and reacting for 1-2 h at 100 ℃.
The invention has the advantages that:
the method provided by the invention uses palladium powder as a raw material to replace palladium chloride in the prior art, so that the reaction cost is reduced, and the prepared product has high purity and high yield.
Detailed Description
Example 1
(1) Dissolving 15g of palladium powder in 45 mL of aqua regia, reacting for 1 h at 100 ℃ to obtain a palladium active group, and mixing with 45 mL of benzonitrile after cooling;
(2) distilling to remove water in the reaction system, then reacting for 3 h at 130 ℃, and removing palladium black by thermal filtration after the reaction is finished;
(3) cooling the filtrate obtained in the step (2), adding the filtrate into 75 mL of n-hexane, separating out yellow solid, filtering, washing a filter cake obtained by filtering with n-hexane, and drying in vacuum to obtain 52.4 g of bis (cyanophenyl) palladium dichloride;
in this example, the yield of bis (cyanophenyl) palladium dichloride was 97%; the detection proves that the content of the metal palladium is 27.55 percent, and the theoretical content of the metal palladium is 27.74 percent. The elemental analysis results were: c,43.85, H, 2.61, N,7.27 and Cl, 18.50. In agreement with the theoretical results (C)14H10Cl2N2Pd, C,43.84, H, 2.63, N,7.30, Cl, 18.48), demonstrating that the resulting product is bis (cyanophenyl) palladium dichloride.
Example 2
(1) Dissolving 15g of palladium powder in 45 mL of aqua regia, reacting for 2 h at 100 ℃ to obtain a palladium active group, and mixing with 75 mL of benzonitrile after cooling;
(2) distilling to remove water in the reaction system, then reacting for 4 hours at 140 ℃, and thermally filtering to remove palladium black after the reaction is finished;
(3) cooling the filtrate obtained in the step (2), adding the filtrate into 75 mL of n-hexane, separating out yellow solid, filtering, washing a filter cake obtained by filtering with n-hexane, and drying in vacuum to obtain 53.1 g of bis (cyanophenyl) palladium dichloride;
in this example, the yield of bis (cyanophenyl) palladium dichloride was 98%; the detection proves that the content of the metal palladium is 27.49 percent, and the theoretical content of the metal palladium is 27.74 percent. The elemental analysis results were: 43.83 percent of C, 2.62 percent of H, 7.28 percent of N, and 18.46 percent of Cl. In agreement with the theoretical results (C)14H10Cl2N2Pd, C,43.84, H, 2.63, N,7.30, Cl, 18.48), proving that the resulting product is bis (cyanobenzene)) Palladium dichloride.
Example 3
(1) Dissolving 15g of palladium powder in 60 mL of aqua regia, reacting for 1.5 h at 100 ℃ to obtain a palladium active group, and mixing with 120 mL of benzonitrile after cooling;
(2) distilling to remove water in the reaction system, then reacting for 3 h at 150 ℃, and removing palladium black by thermal filtration after the reaction is finished;
(3) cooling the filtrate obtained in the step (2), adding the filtrate into 100 mL of n-hexane, separating out yellow solid, filtering, washing a filter cake obtained by filtering with n-hexane, and drying in vacuum to obtain 52.7 g of bis (cyanophenyl) palladium dichloride;
in this example, the yield of bis (cyanophenyl) palladium dichloride was 97%; the detection proves that the content of the metal palladium is 27.51 percent, and the theoretical content of the metal palladium is 27.74 percent. The elemental analysis results were: c,43.82, H, 2.65, N,7.28, Cl, 18.49. In agreement with the theoretical results (C)14H10Cl2N2Pd, C,43.84, H, 2.63, N,7.30, Cl, 18.48), demonstrating that the resulting product is bis (cyanophenyl) palladium dichloride.
Example 4
(1) Dissolving 15g of palladium powder in 60 mL of aqua regia, reacting for 1.5 h at 100 ℃ to obtain a palladium active group, and mixing with 120 mL of benzonitrile after cooling;
(2) distilling to remove water in the reaction system, then reacting for 5 hours at 150 ℃, and removing palladium black by thermal filtration after the reaction is finished;
(3) cooling the filtrate obtained in the step (2), adding the filtrate into 150 mL of n-hexane, separating out yellow solid, filtering, washing a filter cake obtained by filtering with n-hexane, and drying in vacuum to obtain 53.3 g of bis (cyanophenyl) palladium dichloride;
in this example, the yield of bis (cyanophenyl) palladium dichloride was 99%; the detection proves that the content of the metal palladium is 27.46 percent, and the theoretical content of the metal palladium is 27.74 percent. The elemental analysis results were: 43.87 percent of C, 2.64 percent of H, 7.27 percent of N, and 18.46 percent of Cl. In agreement with the theoretical results (C)14H10Cl2N2Pd, C,43.84, H, 2.63, N,7.30, Cl, 18.48), demonstrating that the resulting product is bis (cyanophenyl) palladium dichloride.
Example 5
(1) Dissolving 15g of palladium powder in 50mL of aqua regia, reacting for 2 h at 100 ℃ to obtain a palladium active group, and mixing with 80 mL of benzonitrile after cooling;
(2) distilling to remove water in the reaction system, then reacting for 4 hours at 140 ℃, and thermally filtering to remove palladium black after the reaction is finished;
(3) cooling the filtrate obtained in the step (2), adding the filtrate into 90 mL of petroleum ether, separating out yellow solid, filtering, washing a filter cake obtained by filtering with n-hexane, and drying in vacuum to obtain 53.1 g of bis (cyanophenyl) palladium dichloride;
in this example, the yield of bis (cyanophenyl) palladium dichloride was 99%; the detection proves that the content of the metal palladium is 27.51 percent, and the theoretical content of the metal palladium is 27.74 percent. The elemental analysis results were: c,43.84, H, 2.64, N,7.29 and Cl, 18.47. In agreement with the theoretical results (C)14H10Cl2N2Pd, C,43.84, H, 2.63, N,7.30, Cl, 18.48), demonstrating that the resulting product is bis (cyanophenyl) palladium dichloride.
Example 6
(1) Dissolving 15g of palladium powder in 30 mL of aqua regia, reacting for 2 h at 100 ℃ to obtain a palladium active group, and mixing with 90 mL of benzonitrile after cooling;
(2) distilling to remove water in the reaction system, then reacting for 4 hours at 140 ℃, and thermally filtering to remove palladium black after the reaction is finished;
(3) cooling the filtrate obtained in the step (2), adding the filtrate into 100 mL of n-heptane, separating out yellow solid, filtering, washing a filter cake obtained by filtering with n-hexane, and drying in vacuum to obtain 52.9 g of bis (cyanophenyl) palladium dichloride;
in this example, the yield of bis (cyanophenyl) palladium dichloride was 98%; the detection proves that the content of the metal palladium is 27.54 percent, and the theoretical content of the metal palladium is 27.74 percent. The elemental analysis results were: 43.83 percent of C, 2.64 percent of H, 7.25 percent of N, and 18.46 percent of Cl. In agreement with the theoretical results (C)14H10Cl2N2Pd, C,43.84, H, 2.63, N,7.30, Cl, 18.48), demonstrating that the resulting product is bis (cyanophenyl) palladium dichloride.
Example 7
(1) Dissolving 15g of palladium powder in 30 mL of aqua regia, reacting for 2 h at 100 ℃ to obtain a palladium active group, and mixing with 90 mL of benzonitrile after cooling;
(2) distilling to remove water in the reaction system, then reacting for 5 hours at 150 ℃, and removing palladium black by thermal filtration after the reaction is finished;
(3) cooling the filtrate obtained in the step (2), adding the filtrate into 100 mL of n-pentane, separating out a yellow solid, filtering, washing a filter cake obtained by filtering with n-hexane, and drying in vacuum to obtain 53.2 g of bis (cyanophenyl) palladium dichloride;
in this example, the yield of bis (cyanophenyl) palladium dichloride was 99%; the detection proves that the content of the metal palladium is 27.49 percent, and the theoretical content of the metal palladium is 27.74 percent. The elemental analysis results were: c,43.86, H, 2.64, N,7.27 and Cl, 18.48. In agreement with the theoretical results (C)14H10Cl2N2Pd, C,43.84, H, 2.63, N,7.30, Cl, 18.48), demonstrating that the resulting product is bis (cyanophenyl) palladium dichloride.
Claims (5)
1. A preparation method of bis (cyanophenyl) palladium dichloride is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving palladium powder in aqua regia to prepare a palladium active group, and mixing the palladium active group with benzonitrile after cooling;
(2) distilling to remove water, heating for reaction, and filtering;
(3) and cooling the filtrate, adding the cooled filtrate into an organic solvent, separating out a solid, filtering, washing the obtained filter cake with the organic solvent, and drying in vacuum.
2. The process for preparing bis (cyanophenyl) palladium dichloride according to claim 1 wherein: the organic solvent is any one of n-hexane, petroleum ether, n-heptane and n-pentane.
3. The process for preparing bis (cyanophenyl) palladium dichloride according to claim 2 wherein: the proportion of the palladium powder, the aqua regia, the benzonitrile and the organic solvent is as follows: 1 g: (2-4) mL: (3-8) mL: (5-10) mL.
4. The method for producing bis (cyanophenyl) palladium dichloride according to claim 3, wherein: the heating reaction in the step (2) is carried out at the temperature of 130-150 ℃ for 3-5 h.
5. The method for producing bis (cyanophenyl) palladium dichloride according to claim 4, wherein: the conditions for preparing the palladium active set in the step (1) are as follows: dissolving palladium powder in aqua regia, and reacting for 1-2 h at 100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011506479.8A CN112592372A (en) | 2020-12-18 | 2020-12-18 | Preparation method of bis (cyanobenzene) palladium dichloride |
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| CN202011506479.8A CN112592372A (en) | 2020-12-18 | 2020-12-18 | Preparation method of bis (cyanobenzene) palladium dichloride |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3929773A (en) * | 1973-04-05 | 1975-12-30 | Sumitomo Chemical Co | Process for preparation of a palladium complex compound |
| CN103265581A (en) * | 2013-06-08 | 2013-08-28 | 西安凯立化工有限公司 | Method for preparing bis(diphenylphosphino)alkane palladium dichloride complex |
| CN110759951A (en) * | 2019-11-11 | 2020-02-07 | 西安凯立新材料股份有限公司 | Preparation method of bis (di-tert-butylphosphine) palladium dichloride |
-
2020
- 2020-12-18 CN CN202011506479.8A patent/CN112592372A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3929773A (en) * | 1973-04-05 | 1975-12-30 | Sumitomo Chemical Co | Process for preparation of a palladium complex compound |
| CN103265581A (en) * | 2013-06-08 | 2013-08-28 | 西安凯立化工有限公司 | Method for preparing bis(diphenylphosphino)alkane palladium dichloride complex |
| CN110759951A (en) * | 2019-11-11 | 2020-02-07 | 西安凯立新材料股份有限公司 | Preparation method of bis (di-tert-butylphosphine) palladium dichloride |
Non-Patent Citations (1)
| Title |
|---|
| ALLSCHER, THORSTEN 等: "Sugar-alcohol complexes of palladium(II): on the variable rigidity of open-chain carbohydrate ligands", 《CHEMISTRY - AN ASIAN JOURNAL》 * |
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Application publication date: 20210402 |