CN102786552A - Preparation method of [1,1'-di(diphenyl phosphino) ferrocene] palladium dichloride (dppfPdCl2) - Google Patents
Preparation method of [1,1'-di(diphenyl phosphino) ferrocene] palladium dichloride (dppfPdCl2) Download PDFInfo
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- CN102786552A CN102786552A CN2012102791501A CN201210279150A CN102786552A CN 102786552 A CN102786552 A CN 102786552A CN 2012102791501 A CN2012102791501 A CN 2012102791501A CN 201210279150 A CN201210279150 A CN 201210279150A CN 102786552 A CN102786552 A CN 102786552A
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Abstract
The invention relates to a preparation method of [1,1'-di(diphenyl phosphino) ferrocene] palladium dichloride (dppfPdCl2). The preparation method comprises the following step steps that (a) palladium chloride is added into hydrochloric acid, the materials are heated to 40 to 80 DEG C to be dissolved, and ethanol is added for dilution; (b) di-diphenyl phosphino ferrocene (dppf) accounting for 3.0 to 5.0 times of the mass of the palladium chloride is added into tetrahydrofuran solution, and the materials are heated to 40 to 80 DEG C until the dissolution is completed; and (c) the solution obtained in the step (a) is dripped into the solution obtained in the step (b), after the dripping completion, the heat insulation reaction is carried out at 45 to 80 DEG C for 0.5 to 3 hours, then, the cooling, the filtering, the washing and the vacuum drying are carried out, and dppfPdCl2 red crystals are obtained. The hydrochloric acid is added for replacing metal salts such as potassium chloride, sodium chloride or lithium chloride, the reaction can be easily carried out, the reaction time is shortened, the yield is improved, the content of heteroions in noble metal catalysts is reduced, and the preparation method has the advantages that the steps are simple, the efficiency is high, the product cost is low, and the like.
Description
Technical field
The noble metal catalyst technical field is used in the synthetic field of organic chemical industry, medication chemistry and liquid crystal material that the invention belongs to, and is specifically related to the preparation method of a kind of [1, two (diphenylphosphino) ferrocene of 1'-] palladium chloride.
Background technology
[1, two (diphenylphosphino) ferrocene of 1'-] palladium chloride is widely used in the synthetic field of organic chemical industry, medication chemistry and liquid crystal material as catalyzer.At present, its main compound method has: 1) chloro-palladite (K, Na, Li salt) and dppf reaction method, 2) Palladous chloride and acetonitrile (cyanobenzene) complex compound and dppf ligand exchange method.Method 1 utilizes Palladous chloride and sodium-chlor (Repone K or lithium chloride) reaction to obtain the stronger chloro-palladite of solubility, preparation then [1, two (diphenylphosphino) ferrocene of 1'-] palladium chloride; Though this method has shortened the reaction times, has improved reaction yield, aftertreatment is loaded down with trivial details; Introduce K easily; Na, hetero-ions such as Li cause the catalyzer quality not high; Method 2 used acetonitrile and cyanobenzenes all are great toxicity chemical, and this method long reaction time, and efficient is low.
Summary of the invention
The object of the invention is exactly to provide a kind of consuming time shorter for the defective that overcomes above-mentioned prior art existence, and is simple to operate, the preparation method of lower-cost [1, two (diphenylphosphino) ferrocene of 1'-] palladium chloride.
The technical scheme that the present invention takes: the preparation method of a kind of [1, two (diphenylphosphino) ferrocene of 1'-] palladium chloride (dppfPdCl2) comprises the steps:
(a) Palladous chloride is joined in the concentrated hydrochloric acid, be heated to 40-80 ℃ of dissolving, the hydrochloric acid consumption is 0.2-1.0 a times of Palladous chloride quality, adds alcohol dilution, and amount of ethanol is 10-50 a times of Palladous chloride quality;
(b) the two diphenylphosphino ferrocene (dppf) with 3.0-5.0 times of Palladous chloride quality join in the tetrahydrofuran solution, are heated to 40-80 ℃, and until dissolving, the THF consumption is 20-30 a times of Palladous chloride quality;
(c) drips of solution that step (a) is obtained is added in the solution that step (b) obtains, and dropwises the back 45-80 ℃ of insulation 0.5-3h, cooling then; Filter washing, vacuum-drying; Obtain [1, two (diphenylphosphino) ferrocene of 1'-] palladium chloride red crystals.
Concentration of hydrochloric acid is 12N in the said step (a); Alcoholic acid purity is 50%-100%;
The vacuum-drying temperature is 40-60 ℃ in the said step (c), vacuum tightness 0.04-0.06MPa, and be 6-8h time of drying.
The present invention adds alcohol dilution through commercially available Palladous chloride is dissolved in hydrochloric acid, joins then in the tetrahydrofuran solution that contains two diphenylphosphino ferrocene; Insulation, cooling is filtered; Washing, drying obtain [1, two (diphenylphosphino) ferrocene of 1'-] palladium chloride red crystals.Compared with prior art, the present invention adds metal-salts such as salt acid substitution Repone K, sodium-chlor or lithium chloride, makes reaction carry out more easily; Shortened the reaction times; Improved yield, reduced the content of hetero-ion in the noble metal catalyst, it is simple to have step; Advantages such as efficient is high, and product cost is low.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated.
Embodiment 1:
(a) the 531g Palladous chloride is joined in the 400mL hydrochloric acid, be heated to 50 ℃ of stirrings and make its dissolving, add the dilution of 15L absolute ethyl alcohol, said concentration of hydrochloric acid is 12N;
(b) the two diphenylphosphino ferrocene (dppf) of 2000g are joined in the 15L tetrahydrofuran solution, be heated to 65 ℃, until dissolving;
(c) drips of solution that step (a) is obtained is added in the solution that step (b) obtains; Dropwise the back at 50 ℃ of insulation 2h, cooling crystallization, filtration then, crystal is with absolute ethyl alcohol, THF washing 3 times; Vacuum-drying obtains red crystallization 2195.1g, yield 100%.50 ℃ of vacuum-drying temperature, vacuum tightness 0.06MPa, be 7.5h time of drying.
Embodiment 2
(a) the 531g Palladous chloride is joined in the 300mL hydrochloric acid, be heated to 60 ℃ of stirrings and make its dissolving, add the 10L alcohol dilution, said concentration of hydrochloric acid is 12N; Alcoholic acid purity is 85%;
(b) the two diphenylphosphino ferrocene (dppf) of 1800g are joined in the 12L tetrahydrofuran solution, be heated to 55 ℃, until dissolving;
(c) drips of solution that step (a) is obtained is added in the solution that step (b) obtains, and dropwises the back 65 ℃ of insulations 1.5h, cooling crystallization, filtrations then; Crystal is used absolute ethyl alcohol, THF washing 3 times, vacuum-drying; Obtain red crystallization 2189.3g, yield 99.74%.60 ℃ of vacuum-drying temperature, vacuum tightness 0.04MPa, be 6h time of drying.
Embodiment 3
(a) the 531g Palladous chloride is joined in the 200mL hydrochloric acid, be heated to 75 ℃ of stirrings and make its dissolving, add the 25L alcohol dilution, said concentration of hydrochloric acid is 12N; Alcoholic acid purity is 55%;
(b) the two diphenylphosphino ferrocene (dppf) of 1600g are joined in the 11L tetrahydrofuran solution, be heated to 75 ℃, until dissolving;
(c) drips of solution that step (a) is obtained is added in the solution that step (b) obtains, and dropwises the back 75 ℃ of insulations 0.5h, cooling crystallization, filtrations then; Crystal is used absolute ethyl alcohol, THF washing 3 times, vacuum-drying; Obtain red crystallization 2178.6.3g, yield 99.24%.55 ℃ of vacuum-drying temperature, vacuum tightness 0.05MPa, be 7h time of drying.
Claims (3)
1. one kind [1, two (diphenylphosphino) ferrocene of 1'-] palladium chloride (dppfPdCl
2) the preparation method, it is characterized in that said method comprises the steps:
(a) Palladous chloride is joined in the hydrochloric acid, be heated to 40-80 ℃ of dissolving, the hydrochloric acid consumption is 0.2-1.0 a times of Palladous chloride quality, adds alcohol dilution, and amount of ethanol is 10-50 a times of Palladous chloride quality;
(b) the two diphenylphosphino ferrocene (dppf) with 3.0-5.0 times of Palladous chloride quality join in the tetrahydrofuran solution, are heated to 40-80 ℃, and until dissolving, the THF consumption is 20-30 a times of Palladous chloride quality;
(c) drips of solution that step (a) is obtained is added in the solution that step (b) obtains, and dropwises the back at 45-80 ℃ of insulation reaction 0.5-3h, then cooling; Filter washing, vacuum-drying; Obtain [1, two (diphenylphosphino) ferrocene of 1'-] palladium chloride red crystals.
2. according to the described method of claim 1, it is characterized in that: concentration of hydrochloric acid is 12N in the said step (a); Alcoholic acid purity is 50%-100%.
3. according to the described method of claim 1, it is characterized in that: the vacuum-drying temperature is 40-60 ℃ in the said step (c), vacuum tightness 0.04-0.06MPa, and be 6-8h time of drying.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN111039989A (en) * | 2019-12-16 | 2020-04-21 | 西安凯立新材料股份有限公司 | Preparation method of bis (diphenylphosphino) -palladium dichloride chiral catalyst |
| CN111253446A (en) * | 2019-12-11 | 2020-06-09 | 江苏欣诺科催化剂有限公司 | Preparation method of palladium complex |
| CN112321651A (en) * | 2020-11-09 | 2021-02-05 | 浙江微通催化新材料有限公司 | Preparation method of [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride |
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| CN101503428A (en) * | 2008-12-30 | 2009-08-12 | 西安凯立化工有限公司 | Method for preparing platinum complex |
| CN102603811A (en) * | 2012-02-22 | 2012-07-25 | 西安凯立化工有限公司 | Synthetic method of [1,1'- bis-(diphenyl phosphine) ferrocene] palladium dichloride methylene dichloride complex |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103265581B (en) * | 2013-06-08 | 2016-03-30 | 西安凯立新材料股份有限公司 | A kind of preparation method of two (diphenylphosphine) alkane palladium chloride title complex |
| CN111253446A (en) * | 2019-12-11 | 2020-06-09 | 江苏欣诺科催化剂有限公司 | Preparation method of palladium complex |
| CN111039989A (en) * | 2019-12-16 | 2020-04-21 | 西安凯立新材料股份有限公司 | Preparation method of bis (diphenylphosphino) -palladium dichloride chiral catalyst |
| CN112321651A (en) * | 2020-11-09 | 2021-02-05 | 浙江微通催化新材料有限公司 | Preparation method of [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride |
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Application publication date: 20121121 |