CN105237568A - Preparing method for di-tertiary butyl-4-dimethylamino phenylphosphine and bis(di-tertiary butyl-4-dimethylamino phenylphosphine) palladium chloride - Google Patents
Preparing method for di-tertiary butyl-4-dimethylamino phenylphosphine and bis(di-tertiary butyl-4-dimethylamino phenylphosphine) palladium chloride Download PDFInfo
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Abstract
The invention provides a preparing method for di-tertiary butyl-4-dimethylamino phenylphosphine. Di-tertiary butylphosphine is subjected to low-temperature lithiation under shielding of inert gas and then reacts with N,N-dimethyl p-chloroaniline, and di-tertiary butyl-4-dimethylamino phenylphosphine is obtained. According to the preparing method, di-tertiary butyl-4-dimethylamino phenylphosphine is purified after a quenching reaction. The invention further provides a preparing method for bis(di-tertiary butyl-4-dimethylamino phenylphosphine) palladium chloride. Di-tertiary butyl-4-dimethylamino phenylphosphine obtained through the preparing method is further subjected to complexation with (1,5-cyclooctadiene) palladium dichloride or bispalladium dichloride. A di-tertiary butyl-4-dimethylamino phenylphosphine ligand is prepared through the novel method, purified and then subjected to palladium complexation, and the preparing yield is greatly increased; meanwhile, the loss of palladium is reduced, the preparing cost is greatly reduced, and the obtained products are high in purity and good in quality.
Description
Technical field
The present invention relates to a kind of prepare di-t-butyl-4-dimethylamino phenyl phosphine method and the method for two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride of preparation, belong to technical field of organic synthesis.
Background technology
Two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride plays an important role in modern organic synthesis and practical application, it is used for mainly as catalyzer in the linked reactions such as Suzuki, has and apply very widely in the synthesis of the materials such as liquid crystal material, light functional complexes.Di-t-butyl-4-dimethylamino phenyl phosphine is applied in the preparation process of two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride as middle part.In actual applications, usually to the purity of two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride and quality, there is higher requirement.
Up to now, in order to obtain two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chlorides of high purity, high yield, researchist proposes many improvement projects about two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride preparation method and constantly attempts.Bibliographical information single stage method is had to prepare two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride, specifically use three (dibenzalacetone) two palladium chtalyst di-t-butyl phosphine, potassium tert.-butoxide and N, N-dimethylatedρ-bromoaniline reacts, by obtained di-t-butyl-4-dimethylamino phenyl Phosphine ligands without purification process, directly obtain the finished product with (1,5-cyclooctadiene) palladium chloride complexing.The method reactions steps is few, and control than being easier to, but drawback is because di-t-butyl-4-dimethylamino phenyl Phosphine ligands is without purification process, therefore causes the loss of palladium to increase, and the product purity obtained is low, poor quality, product yield only about 70%.And the method is in the process preparing di-t-butyl-4-dimethylamino phenyl Phosphine ligands, need the expensive palladium catalysts such as use such as three (dibenzalacetone) two palladium, therefore the method preparation cost is higher, causes product price to remain high.
Therefore, seek a kind of method practical more economically and prepare di-t-butyl-4-dimethylamino phenyl Phosphine ligands and two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride, improving it and prepare productive rate and product purity, improve product quality, is one of technical problem urgently to be resolved hurrily.
Summary of the invention
The object of this invention is to provide a kind of preparation method of di-t-butyl-4-dimethylamino phenyl phosphine and the preparation method of two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride, while significantly improve and preparing productive rate, the product purity prepared is high, quality better, preparation cost also significantly reduces.
The invention provides a kind of preparation method of di-t-butyl-4-dimethylamino phenyl phosphine, comprising: di-t-butyl phosphine under protection of inert gas after low temperature lithiation, with N, N-dimethyl to halogen aniline reaction.
According to a concrete but nonrestrictive embodiment of the present invention, described method also comprises: reaction terminates rear quencher reaction, carries out purification process to product.
According to a concrete but nonrestrictive embodiment of the present invention, described method comprises the following steps successively:
Under protection of inert gas, at-10-0 DEG C, in the organic solvent solution of di-t-butyl phosphine, drip butyllithium, at 50-55 DEG C of insulation 6-16 hour;
Reacting liquid temperature is down to-10-0 DEG C, drips N, N-dimethyl to the organic solvent solution of halobenzene amine, at 50-55 DEG C of insulation 6-16 hour;
Reaction solution is down to room temperature, in ice-water bath downhill reaction liquid, drips triethylamine or weak acid and weak base salt brine solution quencher reaction;
Under anhydrous and oxygen-free environment, by supernatant liquid except desolventizing, underpressure distillation, obtains di-t-butyl-4-dimethylamino phenyl phosphine.
According to a concrete but nonrestrictive embodiment of the present invention, wherein N, N-dimethyl is N, N-dimethyl p-Chlorobenzoic acid amide or N, N-dimethylatedρ-bromoaniline to halobenzene amine; The mol ratio of N, N-dimethyl to halobenzene amine and di-t-butyl phosphine can be 1:1-1.5.
According to a concrete but nonrestrictive embodiment of the present invention, wherein the volumetric molar concentration of butyllithium is 1.0M-2.5M; The mol ratio of di-t-butyl phosphine and butyllithium is 1:1-1.5.
According to a concrete but nonrestrictive embodiment of the present invention, wherein the organic solvent of di-t-butyl phosphine lithiumation and the organic solvent of N, N-dimethyl to halobenzene amine are at least one in benzene, toluene or dimethylbenzene.
On the other hand, present invention also offers a kind of preparation method of two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride, comprise: the di-t-butyl-4-dimethylamino phenyl phosphine prepared with aforesaid method and (1,5-cyclooctadiene) palladium chloride complexing obtain.
According to a concrete but nonrestrictive embodiment of the present invention, described method comprises:
Under protection of inert gas, at-10-0 DEG C, in the organic solvent solution of di-t-butyl phosphine, drip butyllithium, at 50-55 DEG C of insulation 6-16 hour;
Reacting liquid temperature is down to-10-0 DEG C, drips N, N-dimethyl to the organic solvent solution of halobenzene amine, at 50-55 DEG C of insulation 6-16 hour;
Reaction solution is down to room temperature, in ice-water bath downhill reaction liquid, drips triethylamine or weak acid and weak base salt brine solution quencher reaction;
Under anhydrous and oxygen-free environment, by supernatant liquid except desolventizing, underpressure distillation, obtains di-t-butyl-4-dimethylamino phenyl phosphine;
Under protection of inert gas; to (1; 5-cyclooctadiene) in palladium chloride and organic solvent; add di-t-butyl-4-dimethylamino phenyl phosphine; react 8-16 hour under room temperature, have solid to separate out, filter; drying, obtains two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride.
According to a concrete but nonrestrictive embodiment of the present invention, wherein the mol ratio of (1,5-cyclooctadiene) palladium chloride and di-t-butyl-4-dimethylamino phenyl phosphine is 1:2-2.5.
According to a concrete but nonrestrictive embodiment of the present invention, wherein the two acetonitrile palladium chloride of (1,5-cyclooctadiene) palladium chloride replaces.
Beneficial effect of the present invention is mainly reflected in:
1. the present invention is in the process of synthesis di-t-butyl-4-dimethylamino phenyl phosphine, have employed a kind of new synthetic route, namely after di-t-butyl phosphine low temperature lithiation, with N, N-dimethyl to halogen aniline reaction.Do not use expensive palladium salt to make catalyzer in this building-up process, significantly reduce preparation cost.
2. the shortcomings such as the yield that the present invention is directed to two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride of final product is low, purity difference, increase and purification process is carried out to intermediate product di-t-butyl-4-dimethylamino phenyl Phosphine ligands, after obtaining pure part, again with (1,5-cyclooctadiene) palladium chloride or two acetonitrile palladium chloride complexing, finally obtain high-quality, high yield, highly purified two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride product, farthest decrease the loss of palladium simultaneously, reduce further preparation cost.
3. the preparation method of two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride of the present invention, reactions steps is few, easily controls, and cost is low, and productive rate is high, and product purity is high, quality better, economical and practical, is very applicable to large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride
1h-NMR.
Fig. 2 is two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride
31p-NMR.
Embodiment
Provided hereinafter concrete embodiment and further illustrate the present invention, but the present invention is not limited only to following embodiment.
The present inventor has found the new synthesis route of a di-t-butyl-4-dimethylamino phenyl phosphine through studying for a long period of time: after di-t-butyl phosphine low temperature lithiation, with N, N-dimethyl, to halogen aniline reaction, can obtain the di-t-butyl-4-dimethylamino phenyl phosphine of high yield.This route be different from completely prior art with three (dibenzalacetone) two palladium chtalyst di-t-butyl phosphine and N, N-dimethyl to the reaction scheme of halobenzene amine.Synthetic route of the present invention, because avoiding using expensive palladium catalyst, significantly reduces preparation cost.
Simultaneously, contriver finds, if the purity of di-t-butyl-4-dimethylamino phenyl Phosphine ligands is not high, following with (1,5-cyclooctadiene) palladium chloride complexing process in, the intermediate products such as the di-t-butyl phosphine that reaction is residual be can and palladium complexing, easily cause the loss of palladium, increase preparation cost, this is also the major reason causing final product low yield, product purity not high.Therefore the present invention after preparing di-t-butyl-4-dimethylamino phenyl Phosphine ligands, adds purification step, obtains by the method for underpressure distillation the complexing that pure part carries out palladium again.The experiment proved that, productivity ratio prior art of the present invention improves about 30%, and product purity and quality also significantly promote.
Therefore the present invention proposes with di-t-butyl phosphine for starting raw material, after low temperature lithiation with N, N-dimethyl to halogen aniline reaction, cancellation, with (1,5-cyclooctadiene) palladium chloride complexing after purified process, obtain two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride.Concrete synthetic route is as follows:
Below each reactions steps is described in detail.
(1) lithiumation of di-t-butyl phosphine
Under the protection of rare gas element as nitrogen; in reaction vessel, add di-t-butyl phosphine and organic solvent as benzene,toluene,xylene etc., drip butyllithium at-10-0 DEG C, drip off at 50-55 DEG C of insulation 6-16 hour; preferred insulation 12-16 hour, obtains the lithiumation thing of di-t-butyl phosphine.
Wherein, butyllithium can be at least one in n-Butyl Lithium, s-butyl lithium or tert-butyl lithium.The volumetric molar concentration of butyllithium can be 1.0M-2.5M, preferred 2.4M-2.5M.The mol ratio of di-t-butyl phosphine and butyllithium can be 1:1-1.5
The amount of the organic solvent of di-t-butyl phosphine lithiumation can need the ratio of 5-10mL organic solvent with reference to 1g di-t-butyl phosphine.
(2) generation of di-t-butyl-4-dimethylamino phenyl phosphine
Reacting liquid temperature is down to-10-0 DEG C, drip N, N-dimethyl to the organic solvent of halobenzene amine as benzene,toluene,xylene solution, at 50-55 DEG C of insulation 6-16 hour after dropwising, preferred insulation 10-16 hour, generates di-t-butyl-4-dimethylamino phenyl phosphine.
Wherein, N, N-dimethyl preferably uses N to halobenzene amine, N-dimethyl p-Chlorobenzoic acid amide or N, N-dimethylatedρ-bromoaniline.
The mol ratio of N, N-dimethyl to halobenzene amine and di-t-butyl phosphine can be 1:1-1.5, preferred 1:1-1.1.
Dissolve N, N-dimethyl can need 5-10mL organic solvent to halobenzene amine with reference to 1gN, N-dimethyl ratio to the amount of the organic solvent of halobenzene amine.
(3) cancellation
Reaction solution is down to room temperature, drips triethylamine under ice-water bath or weak acid and weak base salt brine solution carries out quencher to reaction.Wherein, weak acid and weak base salt brine solution can be aqueous ammonium chloride solution.The mol ratio of N, N-dimethyl to halobenzene amine and triethylamine or weak acid and mild base salt can be 1:0.5-1.
(4) purification process
Under anhydrous and oxygen-free condition, by the supernatant liquid precipitation in reaction flask, except desolventizing, underpressure distillation, collects the cut of 120 DEG C (15mmHg), obtains pure di-t-butyl-4-dimethylamino phenyl phosphine.
Then can with (1,5-cyclooctadiene) palladium chloride complexing, two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride of preparation.
(5) complexation process
Under the protection of rare gas element such as nitrogen; (1 is added in reaction vessel; 5-cyclooctadiene) palladium chloride and organic solvent be as anhydrous tetrahydro furan or anhydrous methyl tetrahydrofuran (THF) etc.; add pure di-t-butyl-4-dimethylamino phenyl phosphine again, react 8-16 hour under room temperature, preferred 10-16 hour; solid is had to separate out; filter, vacuum-drying, obtain two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride.
Wherein, the mol ratio of (1,5-cyclooctadiene) palladium chloride and di-t-butyl-4-dimethylamino phenyl phosphine can be 1:2-2.5.
The amount of dissolving the organic solvent of (1,5-cyclooctadiene) palladium chloride can need the ratio of 5-10mL organic solvent with reference to 1g (1,5-cyclooctadiene) palladium chloride.
(1,5-cyclooctadiene) palladium chloride also can replace with two acetonitrile palladium chloride.
Two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chlorides prepared by the present invention are faint yellow solid powder, yield more than 95%, purity about 99.8%.
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.
Above and the experimental technique used in following embodiment if no special instructions, be ordinary method.
Above and material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
Embodiment one
The preparation of di-t-butyl-4-dimethylamino phenyl phosphine
Reaction flask is replaced as nitrogen atmosphere, 32g di-t-butyl phosphine and 200mL toluene is added in 1L reaction flask, start magnetic agitation,-10 DEG C drip 2.5M n-Butyl Lithium 96mL, drip off and be raised to 50 DEG C of reactions 12 hours, reacting liquid temperature is dropped to-10 DEG C, drip 40gN, the toluene solution 200mL of N-dimethylatedρ-bromoaniline, drip off and be raised to 50 DEG C of reactions 12 hours, afterwards reaction solution is down to room temperature, 10g triethylamine aqueous solution 100mL is dripped under ice-water bath, by upper organic phase under nitrogen protection, precipitation, underpressure distillation, collect 120 DEG C of (15mmHg) di-t-butyl-4-dimethylamino phenyl phosphine 49.2g.
Embodiment two
The preparation of two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride
10g (1 is added in a 500mL reaction, 5-cyclooctadiene) palladium chloride, reaction flask is replaced as nitrogen atmosphere, add di-t-butyl-4-dimethylamino phenyl phosphine 19.6g and the anhydrous tetrahydro furan 200mL of embodiment one preparation, stirring at room temperature 16 hours, solid is had to separate out, filtration drying obtains two (di-t-butyl-4-dimethylamino phenyl phosphine) the Palladous chloride 24.1g of pale yellow powder product, yield is that 97% (yield is based on (1,5-cyclooctadiene) palladium chloride calculating), obtaining product purity by XY-1A intelligence elemental analyser is 99.8%.
Fig. 1 and Fig. 2 is two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chlorides prepared respectively
1h-NMR collection of illustrative plates and
31p-NMR collection of illustrative plates, characterization result is as follows: 400MHz-
1h-NMR (CDCl
3): δ=1.57-1.61 (m, 36H); 2.97 (s, 12H); 6.63-6.65 (d, 4H); 7.70-7.74 (m, 4H).
400MHz-
31P-NMR(CDCl
3):δ＝51.02。
Embodiment three
Reaction flask is replaced as nitrogen atmosphere, 31g di-t-butyl phosphine and 200mL dimethylbenzene is added in 1L reaction flask, start magnetic agitation, 2.5M n-Butyl Lithium 90mL is dripped at 0 DEG C, drip off and be raised to 55 DEG C of reactions 8 hours, reacting liquid temperature is down to-5 DEG C, drip 40gN, the xylene solution 200mL of N-dimethylatedρ-bromoaniline, drip off and be raised to 50 DEG C of reactions 8 hours, afterwards reaction solution is down to room temperature, 6g aqueous ammonium chloride solution 100mL is dripped under ice-water bath, by upper organic phase under nitrogen protection, precipitation, underpressure distillation, collect 120 DEG C of (15mmHg) di-t-butyl-4-dimethylamino phenyl phosphine 48g.
10g (1 is added in another 500mL reacts, 5-cyclooctadiene) palladium chloride, reaction flask is replaced as nitrogen atmosphere, add 19.6g di-t-butyl-4-dimethylamino phenyl phosphine and anhydrous methyl tetrahydrofuran (THF) 200mL, stirring at room temperature 12 hours, solid is had to separate out, filtration drying obtains two (di-t-butyl-4-dimethylamino phenyl phosphine) the Palladous chloride 23.8g of pale yellow powder, (yield is based on (1 for yield 96%, 5-cyclooctadiene) palladium chloride calculating), obtaining product purity by XY-1A intelligence elemental analyser is 99.8%.
Embodiment four
Reaction flask is replaced as nitrogen atmosphere, 30g di-t-butyl phosphine and 200mL benzene is added in 1L reaction flask, start magnetic agitation, 2.5M n-Butyl Lithium 94mL is dripped at-5 DEG C, drip off and be raised to 53 DEG C of reactions 10 hours, reacting liquid temperature is dropped to 0 DEG C, drip 31.1gN, the benzole soln 200mL of N-dimethyl p-Chlorobenzoic acid amide, drip off and be raised to 55 DEG C of reactions 10 hours, afterwards reaction solution is down to room temperature, 10g triethylamine aqueous solution 100mL is dripped under ice-water bath, by upper organic phase under nitrogen protection, precipitation, underpressure distillation, collect 120 DEG C of (15mmHg) di-t-butyl-4-dimethylamino phenyl phosphine 46g.
10g (1 is added in another 500mL reacts, 5-cyclooctadiene) palladium chloride, reaction flask is replaced as nitrogen atmosphere, add 19.6g di-t-butyl-4-dimethylamino phenyl phosphine and anhydrous tetrahydro furan 200mL, stirring at room temperature 10 hours, filtration drying obtains pale yellow powder 23.5g, yield 95%, and obtaining product purity by XY-1A intelligence elemental analyser is 99.8%.
Comparative example
With two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride of art methods preparation
Reaction flask is replaced as nitrogen atmosphere, toluene 200mL is added at 500mL reaction flask, di-t-butyl phosphine 20.5g, potassium tert.-butoxide 23.6g, three (dibenzalacetone) two palladium 3.6g, N, N-dimethylatedρ-bromoaniline 28g, magnetic agitation, 90 DEG C are reacted 12 hours, filtered under nitrogen, precipitation, be added in another 500mL reaction flask, add anhydrous tetrahydro furan 200mL and 10g (1 again, 5-cyclooctadiene) palladium chloride, stirring at room temperature 16 hours, filtration drying obtains pale yellow powder 18.1g, (yield is based on (1 for yield 73%, 5-cyclooctadiene) palladium chloride calculating), obtaining product purity by XY-1A intelligence elemental analyser is 98.1%.
The embodiment of the present invention two compares can obviously find out with above-mentioned comparative example, (1 of same 10g, 5-cyclooctadiene) palladium chloride complexing, the yield of embodiment two improves more than 30% than art methods, and the purity of product is also apparently higher than the product purity of prior art.Therefore, two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chlorides prepared by method of the present invention, beneficial effect is very remarkable.
Below be only embody rule example of the present invention, protection scope of the present invention is not constituted any limitation.The technical scheme that all employing equivalents or equivalence are replaced and formed, all drops within rights protection scope of the present invention.
Claims (10)
1. a preparation method for di-t-butyl-4-dimethylamino phenyl phosphine, comprising: di-t-butyl phosphine under protection of inert gas after low temperature lithiation, with N, N-dimethyl to halogen aniline reaction.
2. method according to claim 1, also comprises: reaction terminates rear quencher reaction, carries out purification process to product.
3. method according to claim 2, comprises the following steps successively:
Under protection of inert gas, at-10-0 DEG C, in the organic solvent solution of di-t-butyl phosphine, drip butyllithium, at 50-55 DEG C of insulation 6-16 hour;
Reacting liquid temperature is down to-10-0 DEG C, drips N, N-dimethyl to the organic solvent solution of halobenzene amine, at 50-55 DEG C of insulation 6-16 hour;
Reaction solution is down to room temperature, in ice-water bath downhill reaction liquid, drips triethylamine or weak acid and weak base salt brine solution quencher reaction;
Under anhydrous and oxygen-free environment, by supernatant liquid except desolventizing, underpressure distillation, obtains di-t-butyl-4-dimethylamino phenyl phosphine.
4., according to method arbitrary in claim 1-3, wherein N, N-dimethyl is N, N-dimethyl p-Chlorobenzoic acid amide or N, N-dimethylatedρ-bromoaniline to halobenzene amine; The mol ratio of N, N-dimethyl to halobenzene amine and di-t-butyl phosphine can be 1:1-1.5.
5. method according to claim 3, wherein the volumetric molar concentration of butyllithium is 1.0M-2.5M; The mol ratio of di-t-butyl phosphine and butyllithium is 1:1-1.5.
6. method according to claim 3, wherein the organic solvent of di-t-butyl phosphine lithiumation and the organic solvent of N, N-dimethyl to halobenzene amine are at least one in benzene, toluene or dimethylbenzene.
7. the preparation method of two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride, comprise: the di-t-butyl-4-dimethylamino phenyl phosphine prepared by claim 1-6 either method and (1,5-cyclooctadiene) palladium chloride complexing obtain.
8. method according to claim 7, comprises the following steps successively:
Under protection of inert gas, at-10-0 DEG C, in the organic solvent solution of di-t-butyl phosphine, drip butyllithium, at 50-55 DEG C of insulation 6-16 hour;
Reacting liquid temperature is down to-10-0 DEG C, drips N, N-dimethyl to the organic solvent solution of halobenzene amine, at 50-55 DEG C of insulation 6-16 hour;
Reaction solution is down to room temperature, in ice-water bath downhill reaction liquid, drips triethylamine or weak acid and weak base salt brine solution quencher reaction;
Under anhydrous and oxygen-free environment, by supernatant liquid except desolventizing, underpressure distillation, obtains di-t-butyl-4-dimethylamino phenyl phosphine;
Under protection of inert gas; to (1; 5-cyclooctadiene) in palladium chloride and organic solvent; add di-t-butyl-4-dimethylamino phenyl phosphine; react 8-16 hour under room temperature, have solid to separate out, filter; drying, obtains two (di-t-butyl-4-dimethylamino phenyl phosphine) Palladous chloride.
9. method according to claim 8, wherein the mol ratio of (1,5-cyclooctadiene) palladium chloride and di-t-butyl-4-dimethylamino phenyl phosphine is 1:2-2.5.
10. the method arbitrary according to claim 7-9, wherein the two acetonitrile palladium chloride of (1,5-cyclooctadiene) palladium chloride replaces.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108659054A (en) * | 2018-07-16 | 2018-10-16 | 陕西瑞科新材料股份有限公司 | A kind of preparation method of dichloro di-t-butyl -4- dimethylaminophenyl phosphine palladiums |
| CN112194685A (en) * | 2020-10-27 | 2021-01-08 | 西安凯立新材料股份有限公司 | Preparation method of [ (S) - (-) -2,2 '-bis (diphenylphosphino) -1,1' -binaphthyl ] palladium dichloride |
| CN114605477A (en) * | 2022-02-28 | 2022-06-10 | 北京格林凯默科技有限公司 | Preparation method of cinnamyl palladium chloride dimer |
| CN114605477B (en) * | 2022-02-28 | 2024-03-12 | 北京格林凯默科技有限公司 | Preparation method of cinnamyl palladium chloride dimer |
| CN114907415A (en) * | 2022-05-10 | 2022-08-16 | 浙江微通催化新材料有限公司 | Preparation method of bis (di-tert-butyl-4-dimethylaminophenylphosphine) palladium chloride |
| CN114907415B (en) * | 2022-05-10 | 2023-12-19 | 浙江微通催化新材料有限公司 | Preparation method of bis (di-tert-butyl-4-dimethylaminophenylphosphine) palladium chloride |
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