CN-121974953-A - Amino phospha phenanthrene compounds diastereoisomeric resolution process

Abstract

The invention provides a method for resolving diastereoisomers of aminophosphine compounds, belonging to the technical field of organic chemistry. The resolution method is realized by utilizing the solubility difference of two groups of diastereoisomers, and a proper amount of aminophosphine compound is added into a common solvent, so that the resolution of the two groups of diastereoisomers of the compound can be realized through simple stirring and filtering operations. Compared with the traditional method, the invention avoids the complicated experimental operation steps and the use of expensive splitting instruments. The splitting step is simple. The diastereoisomer of the amino phosphaphenanthrene compound determines the absolute configuration of molecules through single crystals, has photoluminescence characteristics and aggregation-induced emission effect, and has wide application prospect in the field of photoelectric functional materials.

Inventors

• TANG BENZHONG
• HU RONGRONG
• CHEN LONG

Assignees

• 华南理工大学

Dates

Publication Date

20260505

Application Date

20260316

Claims (6)

1. 1. A method for diastereoisomeric resolution of aminophosphine compounds, comprising the steps of: fully dissolving an aminophosphine compound in an organic solvent, filtering to obtain filtrate and filter cakes respectively, and obtaining two groups of diastereoisomers of the aminophosphine compound; the organic solvent comprises one or more of toluene, tetrahydrofuran, dimethyl sulfoxide, methylene dichloride, chloroform, hydrocarbon organic solvents, alcohol organic solvents, ester organic solvents and amide organic solvents.
2. 2. The method for diastereoisomeric resolution of an aminophosphine compound according to claim 1, wherein the aminophosphine compound has the following structural formula: ; Wherein R 1 and R 2 are independently aryl or aryl derivatives.
3. 3. The method of diastereoisomeric resolution of an aminophosphine according to claim 2, wherein R 1 and R 2 are independently substituted or unsubstituted phenyl; The substituent of the substituted phenyl is alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, nitryl, trifluoromethyl, hydroxyl, carboxyl, halogen atom, amino, phenyl, triphenylamine or tetraphenylvinyl.
4. 4. A method for diastereoisomeric resolution of an aminophosphine compound according to any one of claims 1 to 3, wherein the aminophosphine compound is selected from one of the following compounds: 、 、 、 。
5. 5. the method for diastereoisomeric resolution of an aminophosphine compound according to claim 4, wherein the dosage ratio of the aminophosphine compound to the organic solvent is 0.5-2.0 mmol/2-10 mL.
6. 6. The method for diastereoisomeric resolution of aminophosphine compounds according to claim 1, 2 or 5, wherein the dissolution temperature is 25-80 ℃ and the dissolution time is 4-24 h.

Description

Amino phospha phenanthrene compounds diastereoisomeric resolution process Technical Field The invention relates to the technical field of organic chemistry, in particular to a method for resolving diastereoisomers of aminophosphine compounds. Background The phosphorus-containing compound is an important organic compound and has wide application in the fields of agricultural chemicals, medicines, catalysis, field effect transistors, heat-activated delayed fluorescent materials, flame retardants and the like. Among the phosphorus-containing compounds, phosphorus chiral compounds having a phosphorus chiral center have important research value in the fields of natural products, pharmaceutical chemistry and asymmetric catalysis, and the steric configuration of phosphorus chirality plays a crucial role in the chemical and physical properties of chiral molecules, and interactions between different stereoisomers and chiral receptors often have significant differences, thereby leading to differences in physicochemical properties. For phosphorus-containing chiral stereoisomeric compounds, the biological activity of the recently developed drugs tenofovir alafenamide and adefovir is determined by the absolute stereochemistry of the phosphorus atom. However, the synthesis and separation of the chiral compound still have challenges, and the exploration of the resolution method of the chiral compound containing phosphorus has important significance for the research of the structure-activity relationship and the material design. Unlike enantiomers, which have almost the same physical properties, diastereomers generally exhibit differences in physical properties and chemical reactivity, making separation and resolution of diastereomers possible, and thus becoming the primary method for preparing chiral organophosphorus compounds. By taking advantage of the difference in reactivity and complexation ability of diastereomers of the phosphorus-containing compounds, the corresponding diastereomeric salts, molecular complexes or coordination complexes can be synthesized first, followed by subsequent chiral resolution. Chiral separation of diastereomers can also be achieved by Size Exclusion Chromatography (SEC), chiral High Performance Liquid Chromatography (HPLC), and the like, utilizing their different physicochemical properties. However, the above-mentioned resolution methods often involve cumbersome operation steps, or special instrumentation. Therefore, the development of a simple and efficient separation strategy is not only helpful to deepen the basic understanding of phosphorus stereochemistry, but also provides theoretical guidance for designing functional-oriented phosphorus compounds. Disclosure of Invention The invention aims to provide a method for resolving diastereoisomers of aminophosphine compounds, which is used for solving the technical problems. In order to achieve the above object, the present invention provides the following technical solutions: The invention provides a method for resolving diastereoisomers of aminophosphine compounds, which comprises the following steps: fully dissolving an aminophosphine compound in an organic solvent, filtering to obtain filtrate and filter cakes respectively, and obtaining two groups of diastereoisomers of the aminophosphine compound; the organic solvent comprises one or more of toluene, tetrahydrofuran, dimethyl sulfoxide, methylene dichloride, chloroform, hydrocarbon organic solvents, alcohol organic solvents, ester organic solvents and amide organic solvents. Further, the structural formula of the aminophosphine compound is as follows: ; Wherein R 1 and R 2 are independently aryl or aryl derivatives. Further, the R 1 and R 2 are independently substituted or unsubstituted phenyl; The substituent of the substituted phenyl is alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, nitryl, trifluoromethyl, hydroxyl, carboxyl, halogen atom, amino, phenyl, triphenylamine or tetraphenylvinyl. Further, the aminophosphine compound is selected from one of the following compounds: 、、、。 further, the dosage ratio of the aminophosphine compound to the organic solvent is 0.5-2.0 mmol to 2-10 mL. Further, the dissolution temperature is 25-80 ℃ and the dissolution time is 4-24 hours. The invention has the beneficial effects that: (1) The resolution method of the invention utilizes the difference of diastereoisomer dissolution property of aminophosphine, can realize the separation of two groups of diastereoisomers through simple dissolution and filtration operation, avoids using complex chiral resolution instrument equipment or adding chiral resolution reagent additionally, and greatly reduces the cost of chiral resolution; (2) The preparation method can obtain diastereoisomers of the aminophosphine compound with high yield and high purity, the post-treatment and purification of the resolved product are more thorough, and the process is simple; (3) The preparation method can expan