阅读说明：本技术 一种高纯度磺化binap膦配体的制备方法 (Preparation method of high-purity sulfonated BINAP phosphine ligand ) 是由 王凡 金欣 朱琳 李淑梅 于 2020-06-19 设计创作，主要内容包括：本发明所述的一种高纯度磺化BINAP膦配体(BINAPs)的制备方法,其发明目的在于针对现有的BINAP磺化反应中存在五价态氧化膦(BINAPsO)无法除去的技术缺陷,对磺化BINAP的制备方法进行了技术改进,利用BINAPs和BINAPsO在溶剂乙腈中存在显著的溶解度的差异,在磺化结束后的后处理过程中增加了一个简单、高效的乙腈抽提步骤纯化BINAPs,除掉磺化所产生的五价态的氧化膦副产物,大幅度提高了产品的纯度,制备的BINAPs中的五价氧化膦BINAPsO的摩尔百分含量最低达到5％以下,BINAPs的回收率达到86-97％,并且给出了高质量的BINAPs的核磁共振谱图作为参考。(The invention relates to a preparation method of high-purity sulfonated BINAP phosphine ligands (BINAPs), aiming at the technical defect that pentavalent phosphine oxides (BINAPs) cannot be removed in the existing BINAP sulfonation reaction, the preparation method of the sulfonated BINAP is technically improved, the BINAP and BINAPS O have obvious solubility difference in acetonitrile solvent, a simple and efficient acetonitrile extraction step is added in the post-treatment process after sulfonation is finished to purify the BINAPs, pentavalent phosphine oxides generated by sulfonation are removed, the purity of the product is greatly improved, the mole percentage content of the pentavalent phosphine oxides BINAPS O in the prepared BINAPs is at most below 5%, the recovery rate of the BINAPs reaches 86-97%, and a nuclear magnetic resonance spectrogram of high-quality BINAPs is given as a reference.)

1. A process for preparing a high purity sulfonated BINAP phosphine ligand, comprising: under inert atmosphere, extracting and removing pentavalent phosphine oxide mixed in 2,2 '-bis (diphenylphosphino) -1,1' -binaphthyl-5, 5 '-sodium disulfonate by adopting an acetonitrile solvent extraction method, wherein the structures of 2,2' -bis (diphenylphosphino) -1,1 '-binaphthyl-5, 5' -sodium disulfonate (BINAPs) and phosphine oxide (BINAPSO) thereof are as follows:

wherein BINAPs or BINAPSO have a steric configuration of S-type or R-type.

2. The process of claim 1 for the preparation of a high purity sulfonated BINAP phosphine ligand, comprising: the inert atmosphere is argon or nitrogen.

3. The process of claim 1 for the preparation of a high purity sulfonated BINAP phosphine ligand, comprising: the operation temperature for extracting and removing mixed pentavalent phosphine oxide (BINAPSO) in 2,2' -bis (diphenylphosphino) -1,1' -binaphthyl-5, 5' -sodium disulfonate (BINAPs) by adopting an acetonitrile solvent extraction method is 20-80 ℃.

4. The process of claim 1 for the preparation of a high purity sulfonated BINAP phosphine ligand, comprising: the operation temperature for extracting and removing mixed pentavalent phosphine oxide (BINAPSO) in 2,2' -bis (diphenylphosphino) -1,1' -binaphthyl-5, 5' -sodium disulfonate (BINAPs) by adopting an acetonitrile solvent extraction method is 20-40 ℃.

5. The process of claim 1 for the preparation of a high purity sulfonated BINAP phosphine ligand, comprising: the operation time for extracting and removing mixed pentavalent phosphine oxide (BINAPSO) in 2,2' -bis (diphenylphosphino) -1,1' -binaphthyl-5, 5' -sodium disulfonate (BINAPs) by adopting an acetonitrile solvent extraction method is 0.5-5 h.

6. The process of claim 1 for the preparation of a high purity sulfonated BINAP phosphine ligand, comprising: the operation time for extracting and removing mixed pentavalent phosphine oxide (BINAPSO) in 2,2' -bis (diphenylphosphino) -1,1' -binaphthyl-5, 5' -sodium disulfonate (BINAPs) by adopting an acetonitrile solvent extraction method is 1-2 h.

7. The process of claim 1 for the preparation of a high purity sulfonated BINAP phosphine ligand, comprising: extracting and removing pentavalent phosphine oxide (BINAPSO) mixed in 2,2' -bis (diphenylphosphino) -1,1' -binaphthyl-5, 5' -sodium disulfonate (BINAPs) by adopting an acetonitrile solvent extraction method, wherein the ratio of the mass (g) of the substance to be extracted to the volume (mL) of acetonitrile is 1:10-1: 100.

8. The process of claim 1 for the preparation of a high purity sulfonated BINAP phosphine ligand, comprising: extracting and removing pentavalent phosphine oxide (BINAPSO) mixed in 2,2' -bis (diphenylphosphino) -1,1' -binaphthyl-5, 5' -sodium disulfonate (BINAPs) by adopting an acetonitrile solvent extraction method, wherein the ratio of the mass (g) of the substance to be extracted to the volume (mL) of acetonitrile is 1:30-1: 60.

9. The process of claim 1 for the preparation of a high purity sulfonated BINAP phosphine ligand, comprising: under argon atmosphere, mixing BINAPs mixed with BINAPSO to be extracted with acetonitrile solvent, wherein the ratio of the mass (g) of the substance to be extracted to the volume (mL) of acetonitrile is 1:30-1:60, extracting at 30 ℃ for 2h, then filtering, and drying the filter cake to obtain high-purity BINAPs.

10. The process of claim 1 for the preparation of a high purity sulfonated BINAP phosphine ligand, comprising: mixing BINAPs mixed with BINAPSO to be extracted with acetonitrile solvent in an argon atmosphere, extracting at 30 ℃ for 1h with the ratio of the mass (g) of the extract to the volume (mL) of acetonitrile being 1:20-1:40, and filtering; and adding acetonitrile into the filter cake again until the ratio of the mass (g) of the extract to the volume (mL) of the acetonitrile is 1:20-1:40, extracting for 1h at 30 ℃, filtering, and drying the filter cake to obtain the high-purity BINAPs.

Technical Field

The invention relates to the technical field of chemistry and chemical engineering, in particular to a preparation method of a high-purity sulfonated BINAP phosphine ligand.

Background

Noyori designed and synthesized a peptide having C since the beginning of the eighties of the last century₂The application of BINAP diphosphine ligand in asymmetric catalysis has been greatly successful in both academic and industrial production since the atropisomeric chiral diphosphine ligand 2,2 '-bis (diphenylphosphino) -1,1' -Binaphthyl (BINAP) of the axis of symmetry. Chiral BINAP transition metal (Rh, Ru, Ir, etc.) complex has very high catalytic activity and enantioselectivity, but it is mainly used in industryHomogeneous catalysis, where the difficult separation and recycling of expensive chiral noble metal catalysts, has always limited the large-scale industrial application of BINAP.

In recent years, the development of a water/organic two-phase asymmetric catalytic system solves the problems of separation and recycling of a homogeneous chiral noble metal catalyst, and the key point for constructing the water/organic two-phase asymmetric catalytic system is to develop a water-soluble chiral phosphine ligand, wherein the introduction of a sulfonic group into a phosphine ligand molecule through a sulfonation reaction on an aromatic ring is a simple and effective method for preparing the water-soluble phosphine ligand.

Currently, only four patents (JP1991000331535, EP92310561.3, US5274146 and US5324861) disclosed by japan high sand company have been reported in the research aiming at introducing a sulfonic acid group (sodium 2,2' -bis (diphenylphosphino) -1,1' -binaphthyl-5, 5' -disulfonate, hereinafter abbreviated as BINAPs) to the naphthalene ring of BINAPs, but the above patents have a problem of low yields of BINAPs, and the purity of BINAPs has not been analyzed, and a method for purifying BINAPs and a nuclear magnetic spectrum have not been provided.

The present inventors have found that synthesis of BINAPs according to the process of the above patent produces a large amount of by-product of pentavalent phosphine oxide, and the purity of the target product BINAPs is low. Therefore, the main factor affecting the purity of BINAPs is the pentavalent phosphine oxide (BINAPsO) mixed with BINAPs in BINAPs, and no method for removing the pentavalent phosphine oxide in BINAPs is reported in all the published documents at present. Because the purity of the sulfonated BINAP is a key influencing the catalytic performance of the sulfonated BINAP, how to improve the purity of the BINAP is a problem to be solved in water/organic two-phase asymmetric catalysis.

Disclosure of Invention

The invention relates to a preparation method of high-purity sulfonated BINAP phosphine ligand, aiming at solving the technical defect that the pentavalent phosphine oxide cannot be removed in the existing BINAP sulfonation reaction, the invention technically improves the preparation method of sulfonated BINAP published by Nissan high sand company, and utilizes the obvious solubility difference of BINAP and BINAPS O in acetonitrile solvent (BINAP is difficult to dissolve in acetonitrile, BINAPS O is easy to dissolve in acetonitrile), and adds a step of acetonitrile extraction in the post-treatment process after sulfonation is finished, so as to remove pentavalent phosphine oxide byproduct generated by sulfonation, thereby greatly improving the purity of the product and giving high-quality nuclear magnetic spectrum as reference.

The invention relates to a preparation method of a high-purity sulfonated BINAP phosphine ligand, which is characterized in that under inert atmosphere, acetonitrile solvent extraction is adopted to extract and remove mixed pentavalent phosphine oxide in 2,2 '-bis (diphenylphosphino) -1,1' -binaphthyl-5, 5 '-sodium disulfonate, wherein 2,2' -bis (diphenylphosphino) -1,1 '-binaphthyl-5, 5' -sodium disulfonate (BINAPs) and phosphine oxide (BINAPSO) thereof have the following structures:

wherein BINAPs or BINAPSO have a steric configuration of S-type or R-type.

The preparation method of the high-purity sulfonated BINAP phosphine ligand adopts argon or nitrogen as inert atmosphere.

The preparation method of the high-purity sulfonated BINAP phosphine ligand adopts an acetonitrile solvent extraction method to extract and remove pentavalent phosphine oxide (BINAPSO) mixed in 2,2' -bis (diphenylphosphino) -1,1' -binaphthyl-5, 5' -disulfonic Acid Sodium (BINAPs), and the operation temperature is 20-80 ℃.

The preparation method of the high-purity sulfonated BINAP phosphine ligand adopts an acetonitrile solvent extraction method to extract and remove pentavalent phosphine oxide (BINAPSO) mixed in 2,2' -bis (diphenylphosphino) -1,1' -binaphthyl-5, 5' -disulfonic Acid Sodium (BINAPs), and the operation temperature is 20-40 ℃.

The preparation method of the high-purity sulfonated BINAP phosphine ligand adopts an acetonitrile solvent extraction method to extract and remove mixed pentavalent phosphine oxide (BINAPSO) in 2,2' -bis (diphenylphosphino) -1,1' -binaphthyl-5, 5' -disulfonic Acid Sodium (BINAPs), and the operation time is 0.5-5 h.

The preparation method of the high-purity sulfonated BINAP phosphine ligand adopts an acetonitrile solvent extraction method to extract and remove mixed pentavalent phosphine oxide (BINAPSO) in 2,2' -bis (diphenylphosphino) -1,1' -binaphthyl-5, 5' -disulfonic Acid Sodium (BINAPs), and the operation time is 1-2 h.

The invention relates to a preparation method of a high-purity sulfonated BINAP phosphine ligand, which adopts an acetonitrile solvent extraction method to extract and remove mixed pentavalent phosphine oxide (BINAPSO) in 2,2' -bis (diphenylphosphino) -1,1' -binaphthyl-5, 5' -sodium disulfonate (BINAPs), wherein the ratio of the mass (g) of a substance to be extracted to the volume (mL) of acetonitrile is 1:10-1: 100.

The invention relates to a preparation method of a high-purity sulfonated BINAP phosphine ligand, which adopts an acetonitrile solvent extraction method to extract and remove mixed pentavalent phosphine oxide (BINAPSO) in 2,2' -bis (diphenylphosphino) -1,1' -binaphthyl-5, 5' -sodium disulfonate (BINAPs), wherein the ratio of the mass (g) of a substance to be extracted to the volume (mL) of acetonitrile is 1:30-1: 60.

The preparation method of the high-purity sulfonated BINAP phosphine ligand is characterized by mixing BINAPs to be extracted and mixed with BINAPS O with an acetonitrile solvent in an argon atmosphere, extracting for 2h at 30 ℃ with the ratio of the mass (g) of the extract to the volume (mL) of acetonitrile, filtering, and drying a filter cake to obtain the high-purity BINAPs.

The preparation method of the high-purity sulfonated BINAP phosphine ligand is characterized by mixing BINAPs to be extracted and mixed with BINAPSO with an acetonitrile solvent under the argon atmosphere, extracting for 1h at 30 ℃ and then filtering, wherein the ratio of the mass (g) of the extract to the volume (mL) of acetonitrile is 1:20-1: 40; and adding acetonitrile into the filter cake again until the ratio of the mass (g) of the extract to the volume (mL) of the acetonitrile is 1:20-1:40, extracting for 1h at 30 ℃, filtering, and drying the filter cake to obtain the high-purity BINAPs.

Compared with the prior art of the Japanese high sand company, the preparation method of the high-purity sulfonated BINAP phosphine ligand has the following remarkable technical progress:

1. preparation of high purity BINAPs: according to the preparation method of the high-purity sulfonated BINAP phosphine ligand, the mole percentage content of the pentavalent phosphine oxide BINAPS O in the prepared BINAPs is as low as less than 5%; while the japanese high sand company patent does not disclose the phosphine oxide content in BINAPs.

2. The purification method is simple and efficient: purifying BINAPs by a simple and efficient acetonitrile extraction method, wherein the recovery rate of the BINAPs reaches 86-97%; while the Japanese high sand company patent does not disclose a method for purifying BINAPs.

3. High-quality nuclear magnetic spectrum: according to the preparation method of the high-purity sulfonated BINAP phosphine ligand, the mole percentage of the pentavalent phosphine oxide BINAPSO in BINAPs is less than 5%, so that the nuclear magnetic hydrogen spectrum, the carbon spectrum and the phosphorus spectrum of the BINAPs with high quality can be provided; while the Japanese high sand company patent does not disclose the nuclear magnetic spectrum of BINAPs.

Drawings

In order to more clearly illustrate the technical solution of the present invention, the drawings used in the description of the prior art will be briefly introduced below.

FIG. 1: FT-IR spectrogram of sodium 2,2' -bis (diphenylphosphino) -1,1' -binaphthyl-5, 5' -disulfonate

FIG. 2 is a drawing: process for preparing sodium 2,2' -bis (diphenylphosphino) -1,1' -binaphthyl-5, 5' -disulfonate¹H NMR spectrum

FIG. 3: process for preparing sodium 2,2' -bis (diphenylphosphino) -1,1' -binaphthyl-5, 5' -disulfonate¹³C NMR spectrum

FIG. 4 is a drawing: process for preparing sodium 2,2' -bis (diphenylphosphino) -1,1' -binaphthyl-5, 5' -disulfonate³¹P NMR spectrum

FIG. 5: HR-MS spectrogram of 2,2' -bis (diphenylphosphino) -1,1' -binaphthyl-5, 5' -disulfonic acid sodium

Detailed Description

The following examples are intended to illustrate the present invention without further limiting it, and equivalents and modifications made using the technical idea of the present invention are still within the scope of the present invention.