阅读说明：本技术 一种1,1′-双（二叔丁基膦基）二茂铁二氯化钯的制备方法 (Preparation method of 1,1' -bis (di-tert-butylphosphino) ferrocene palladium dichloride ) 是由 校大伟 万克柔 李小安 高武 于 2019-11-11 设计创作，主要内容包括：本发明公开一种1,1’-双(二叔丁基膦基)二茂铁二氯化钯的制备方法,包括以下步骤：(1)将1,1’-双(二叔丁基膦基)二茂铁和有机溶剂混合,在氮气氛围下、50-70℃下搅拌至澄清；(2)向步骤(1)的产物中一次性加入双(乙腈)氯化钯(II),在氮气氛围下、30-70℃下搅拌反应3-6h,然后冷却搅拌结晶,过滤,滤饼真空干燥后,即可。本发明提供的方法,以1,1’-双(二叔丁基膦基)二茂铁为配体,双(乙腈)氯化钯(II)为前驱体,制备方法简单,产物的收率高。(The invention discloses a preparation method of 1,1' -bis (di-tert-butyl phosphino) ferrocene palladium dichloride, which comprises the following steps: (1) mixing 1,1' -bis (di-tert-butyl phosphino) ferrocene and an organic solvent, and stirring the mixture at 50-70 ℃ in a nitrogen atmosphere until the mixture is clear; (2) and (2) adding bis (acetonitrile) palladium (II) chloride into the product obtained in the step (1) at one time, stirring and reacting for 3-6h at 30-70 ℃ in a nitrogen atmosphere, cooling, stirring, crystallizing, filtering, and drying a filter cake in vacuum. The method provided by the invention takes 1,1' -bis (di-tert-butyl phosphino) ferrocene as a ligand and bis (acetonitrile) palladium chloride (II) as a precursor, and has the advantages of simple preparation method and high yield of the product.)

1. A preparation method of 1,1' -bis (di-tert-butyl phosphino) ferrocene palladium dichloride is characterized by comprising the following steps: the method comprises the following steps:

(1) mixing 1,1' -bis (di-tert-butyl phosphino) ferrocene and an organic solvent, and stirring the mixture at 50-70 ℃ in a nitrogen atmosphere until the mixture is clear;

(2) and (2) adding bis (acetonitrile) palladium (II) chloride into the product obtained in the step (1) at one time, stirring and reacting for 3-6h at 30-70 ℃ in a nitrogen atmosphere, cooling, stirring, crystallizing, filtering, and drying a filter cake in vacuum.

2. The method for preparing 1,1' -bis (di-tert-butylphosphino) ferrocene palladium dichloride according to claim 1, wherein: the organic solvent is any one of tetrahydrofuran, absolute ethyl alcohol, methanol and methyl tetrahydrofuran.

3. The method for preparing 1,1' -bis (di-tert-butylphosphino) ferrocene palladium dichloride according to claim 1 or 2, wherein: the mass ratio of the 1,1' -bis (di-tert-butyl phosphino) ferrocene to the organic solvent is 1: (4-10); the mass ratio of the bis (acetonitrile) palladium (II) chloride to the 1,1' -bis (di-tert-butylphosphino) ferrocene is 1: (1.8-2.2).

4. The method for preparing 1,1' -bis (di-tert-butylphosphino) ferrocene palladium dichloride according to claim 1 or 2, wherein: in the step (4), the cooling, stirring and crystallizing are carried out for 2-3h at the temperature of 5-10 ℃.

5. The method for preparing 1,1' -bis (di-tert-butylphosphino) ferrocene palladium dichloride according to claim 1 or 2, wherein: in the step (4), the vacuum drying temperature is 40-60 ℃, the time is 4-8h, and the pressure is 0.08-0.09 MPa.

Technical Field

The invention belongs to the technical field of noble metal catalyst preparation, and particularly relates to a preparation method of 1,1' -bis (di-tert-butylphosphino) ferrocene palladium dichloride.

Background

1,1 '-bis (di-tert-butylphosphino) ferrocene palladium dichloride, also known as dichloro [1,1' -bis (er-tert-butylphosphino) ferrocene palladium (II), is an important metal palladium catalyst, provides a simple and efficient path for C-C, C-N and the like which are difficult to construct under common conditions, and has excellent performance in coupling reactions such as Suzuki reaction, Heck and the like. The reaction has wide application in the aspects of organic drug synthesis, liquid crystal materials, functional materials, compounds with biological activity and the like.

The prior art mainly adopts direct coordination reaction of ligand and metal, has low yield, can not effectively utilize the metal, and has low purity of the obtained product. The process utilizes acetonitrile palladium as a reaction metal precursor, the obtained product has high yield and good quality, and the preparation cost is greatly reduced.

Disclosure of Invention

The invention provides a preparation method of 1,1' -bis (di-tert-butyl phosphino) ferrocene palladium dichloride, which comprises the steps of taking bis (acetonitrile) palladium chloride (II) as a precursor, directly mixing and reacting with ligand 1,1' -bis (di-tert-butyl phosphino) ferrocene, crystallizing, filtering and drying to obtain the 1,1' -bis (di-tert-butyl phosphino) ferrocene palladium dichloride, and the product yield is high.

A preparation method of 1,1' -bis (di-tert-butylphosphino) ferrocene palladium dichloride comprises the following steps:

(1) mixing 1,1' -bis (di-tert-butyl phosphino) ferrocene and an organic solvent, and stirring the mixture at 50-70 ℃ in a nitrogen atmosphere until the mixture is clear;

(2) and (2) adding bis (acetonitrile) palladium (II) chloride into the product obtained in the step (1) at one time, stirring and reacting for 3-6h at 30-70 ℃ in a nitrogen atmosphere, cooling, stirring, crystallizing, filtering, and drying a filter cake in vacuum.

Preferably, the organic solvent is any one of tetrahydrofuran, absolute ethyl alcohol, methanol and methyl tetrahydrofuran.

Preferably, the mass ratio of the 1,1' -bis (di-tert-butyl phosphino) ferrocene to the organic solvent is 1: (4-10); the mass ratio of the bis (acetonitrile) palladium (II) chloride to the 1,1' -bis (di-tert-butylphosphino) ferrocene is 1: (1.8-2.2).

Preferably, the cooling stirring crystallization in the step (4) is stirring at 5-10 ℃ for 2-3 h.

Preferably, the vacuum drying in the step (4) is carried out at the temperature of 40-60 ℃, the time of 4-8h and the pressure of 0.08-0.09 MPa.

The invention has the advantages that:

according to the method provided by the invention, 1' -bis (di-tert-butyl phosphino) ferrocene is used as a ligand, bis (acetonitrile) palladium chloride (II) is used as a precursor, and the target product 1,1' -bis (di-tert-butyl phosphino) ferrocene palladium dichloride can be obtained through crystallization, filtration and drying after the reaction of the 1,1' -bis (di-tert-butyl phosphino) ferrocene ligand and the precursor.

Detailed Description