Method for synthesizing trivalent phosphorus compound from tris (1, 1, 1, 3, 3, 3-hexafluoro-2-propyl) phosphite

Abstract

The invention discloses a method for synthesizing a trivalent phosphorus compound from tris (1, 1, 1, 3, 3, 3-hexafluoro-2-propyl) phosphite, and belongs to the technical field of acyclic, carbocyclic or heterocyclic compounds of phosphorus elements. The method comprises the following steps: taking tri (1, 1, 1, 3, 3, 3-hexafluoro-2-propyl) phosphite as a phosphorus transfer reagent, mixing the tri (1, 1, 1, 3, 3-hexafluoro-2-propyl) phosphite with a nucleophilic reagent, an alkaline reagent and an organic solvent, and carrying out nucleophilic reaction to obtain a crude reaction solution; purifying the crude reaction liquid, and collecting a product to obtain a trivalent phosphorus compound; the nucleophilic reagent comprises at least one of an alcohol compound and a halide thereof, a phenolic compound, an amine compound and an organic metal reagent; the alkaline reagent comprises at least one of organic alkali and salt which is ionized to be alkaline in a solution environment. The method has the advantages of being good in substrate applicability, simple, efficient, green and environmentally friendly, and has a good application prospect in industrial production.

Description

Technical Field

[0001] The invention relates to the technical field of acyclic, carbocyclic or heterocyclic compounds of phosphorus element, and in particular to a method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite. Background Art

[0002] Trivalent phosphorus compounds are a very important class of bulk chemicals, widely used in flame retardants, ligands, plasticizers and other new functional and structural materials. In addition, trivalent phosphorus compounds are also used to prepare environmentally friendly organic chemical raw materials, which have potential application value in dyes, pesticides, cosmetics, pharmaceutical industries and as preservatives.

[0003] The traditional method for synthesizing trivalent phosphorus compounds usually involves first synthesizing an organic phosphorus transfer reagent such as phosphorus trichloride or phosphine, which is then attacked by a nucleophilic reagent to generate the target product. For example, the literature (Donath, M., Schwedtmann, K., Schneider, T. et al. Direct conversion of white phosphorus to versatilephosphorus transfer reagents via oxidative onioation. Nat. Chem. 14, 384–391 (2022).) uses this synthetic route to complete the preparation. The substrate applicability of this method is narrow, and its process involves multiple synthesis steps. Due to the influence of factors such as cumulative errors and accumulation of side reactions, it will inevitably cause raw material losses and reduce the final yield of the product. At the same time, phosphine and chlorine required to generate phosphorus trichloride are both highly biologically toxic, posing a threat to operators and the environment. A large amount of hydrogen chloride is released during the reaction process, which also seriously pollutes the environment and corrodes the equipment.

[0004] In addition to the traditional synthesis method, those skilled in the art have explored other synthesis routes. For example, the Chinese invention patent with publication number CN102702267A discloses a method for preparing a novel and efficient phosphite antioxidant, which uses phosphite triester, pentaerythritol and fatty alcohol as raw materials, and obtains fatty alcohol-based pentaerythritol diphosphite with high phosphorus content by ester exchange in the presence of a catalyst. However, the invention has a narrow scope of application and cannot meet the production needs of synthesizing different trivalent phosphorus compounds.

[0005] For another example, the Chinese invention patent with publication number CN116273160A discloses a catalyst for preparing trivalent phosphorus compounds from pentavalent phosphorus compounds. The catalyst is used in the reaction of preparing trivalent phosphorus compounds from pentavalent phosphorus compounds, and metallic iron or iron-containing metal materials are used as reducing agents to achieve the reduction of pentavalent phosphorus compounds at a temperature not higher than 100°C, and prepare trivalent phosphorus compounds or trivalent phosphorus iron complexes with high yields. However, the invention requires the use of reducing agents and catalysts of specific structures. In its reaction path, the substrate first forms an intermediate under the action of an activator, and then reacts under the action of a catalyst to form a target product. There are many reaction raw materials involved, and the steps are relatively cumbersome. The redox reaction also places higher requirements on the device, which limits its further application in industrial production.

[0006] In summary, the synthesis methods of trivalent phosphorus compounds in the prior art usually have the disadvantages of narrow substrate applicability, cumbersome steps, poor environmental protection, strong corrosion to production equipment, etc. Therefore, providing a method for synthesizing trivalent phosphorus compounds with simple and mild reactions, good applicability and environmental protection is of great significance for expanding its application in the fields of functional materials and medicine. Summary of the invention

[0007] In view of the above-mentioned defects of the prior art, in the first aspect of the present invention, a method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite is provided, which has good substrate applicability, is simple, efficient, and is green and environmentally friendly, and comprises the following steps: tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite is used as a phosphorus transfer reagent, and is mixed with a nucleophilic reagent, an alkaline reagent, and an organic solvent under an inert atmosphere to carry out a nucleophilic reaction to obtain a crude reaction solution; the crude reaction solution is purified, and the product is collected to obtain a trivalent phosphorus compound; The nucleophilic reagent includes at least one of alcohol compounds and halides thereof, phenol compounds, amine compounds, and organic metal reagents.

[0008] Preferably, the alcohol compound includes C 1 -C 5 At least one of the monohydric alcohol and polyhydric alcohol, the phenolic compound includes phenol and its C 1 -C 4 At least one of alkyl substituents, the amine compound includes at least one of aromatic primary amines and heterocyclic secondary amines, and the organometallic reagent includes at least one of a hydrocarbon metal reagent and an aryl metal reagent; The alkaline reagent includes at least one of an organic base and a salt that is alkaline when ionized in a solution environment, and plays a role in promoting the dehydrogenation of the nucleophilic reagent and promoting the nucleophilic attack during the reaction.

[0009] Further preferably, the alcohol compound includes at least one of methanol, ethanol, isopropanol, n-butanol, tert-butanol and pentaerythritol; and the halogenated alcohol compound includes 2-bromoethanol.

[0010] Further preferably, the phenolic compound includes at least one of phenol, p-cresol and 2,4-di-tert-butylphenol.

[0011] Further preferably, the amine compound includes at least one of aniline, benzylamine and morpholine.

[0012] Further preferably, the organometallic reagent includes at least one of allylmagnesium bromide, phenylmagnesium bromide and cyclohexylmagnesium bromide.

[0013] Further preferably, the alkaline reagent includes at least one of 4-methoxypyridine, 4-methylpyridine, 4-dimethylaminopyridine, potassium tert-butoxide, triethylamine, potassium carbonate, and sodium carbonate.

[0014] The organic solvent is used to promote the dispersion of substances and create a solution environment suitable for the reaction. The type of organic solvent can affect the final yield of the product. Based on the type of substrate for the reaction, as presented in one or more embodiments of the present invention, dimethyl sulfoxide, acetonitrile, toluene, tetrahydrofuran, chloroform, dichloromethane, and dichloroethane are suitable choices, which are conducive to improving the yield.

[0015] Preferably, the organic solvent includes at least one of dimethyl sulfoxide, acetonitrile, toluene, tetrahydrofuran, chloroform, dichloromethane and dichloroethane.

[0016] Preferably, the amount of tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite added is 0.5 mmol; the amount of the nucleophilic reagent added is 1-20 mmol; the amount of the alkaline reagent added is 0.02-5 mmol; and the amount of the organic solvent added is 1-10 mL.

[0017] The invention uses tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite as a phosphorus transfer reagent, has good reactivity between substrates, and the nucleophilic reaction can be carried out in a wide temperature range to synthesize the target product.

[0018] Preferably, the temperature of the nucleophilic reaction is 0-120°C, and the reaction time is 0.2-12 h.

[0019] It should be noted that in actual operation, due to the high reactivity of organometallic reagents, for safety reasons, the organometallic reagents should be mixed with other raw materials at low temperature (such as -78 ° C, etc.) to prevent violent heat release and reduce the stability of the system. In addition, when more than one nucleophilic reagent is used for the reaction, it is appropriate to add the nucleophilic reagents in sequence to reduce the formation of by-products and increase the yield. The entire synthesis process should be regarded as a nucleophilic reaction of each nucleophilic reagent with the group in tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite.

[0020] The present invention has no special requirements for the purification and collection process of the product, and can be achieved by using common methods in the art. For example, the organic solvent can be removed by vacuum distillation, and various trivalent phosphorus compounds can be obtained by column chromatography separation and purification; or the crude reaction solution can be distilled and condensed at low temperature to collect the target product. Those skilled in the art can select a suitable method according to actual conditions.

[0021] The reaction equation for the nucleophilic reaction is as follows: ; In the formula, Nu represents a nucleophilic group (representing only a broad category of nucleophilic groups, the specific types may be the same or different); R represents a hydrogen atom or a metal group.

[0022] Based on the above technical scheme, the inventive concept and principle of the present invention is that tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite has good reactivity with nucleophiles, and the types of nucleophiles are wide. Therefore, using tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite as a phosphorus transfer reagent, alcohols, phenols, amines, and organometallic reagents can be used as substrates, and nucleophilic groups in nucleophiles are introduced into the nucleophiles through a one-step reaction in trivalent phosphorus, thereby forming multiple types of trivalent phosphorus compounds. The substrate of this path has a wide range of applications, good selectivity, and high atomic utilization. No highly corrosive raw materials are used in the steps, and no violent redox reactions are involved, which has the advantages of mildness, low pollution, and weak corrosion to the device. In addition, there are few side reactions in the path, and the by-products are hexafluoroisopropanol compounds, which have good recycling value and meet the requirements of green synthesis.

[0023] Compared with the prior art, the present invention has the following advantages and beneficial effects: The invention provides a method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, which has the advantages of good substrate applicability, simplicity, high efficiency, and green environmental protection, and has good application prospects in industrial production. DETAILED DESCRIPTION

[0024] The present invention is further described below by way of examples, but the present invention is not limited to the scope of the examples. The experimental methods in the following examples without specifying specific conditions are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0025] Example 1 The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite comprises the following steps:

[0026] In an argon atmosphere, 0.5 mmol tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, 7.5 mmol n-butanol, 0.3 mmol 4-dimethylaminopyridine (DMAP) and 3 mL dichloroethane (DCE) were added to a Schlenck tube and mixed. The mixture was stirred at room temperature (rt) for 2 h for nucleophilic reaction. After the reaction, the triester phosphite was easily oxidized or hydrolyzed in the air. To protect it, sulfur powder was added to stabilize it before separation. The crude reaction solution was distilled under reduced pressure to remove dichloroethane. The target trivalent phosphorus compound was obtained after purification by column chromatography with a product yield of 76%.

[0027] 1 H NMR (400 MHz, Chloroform-d) δ 4.08 – 3.97 (dt, J = 8.7, 6.5 Hz, 6H), 1.73 – 1.58 (dq, J = 8.3, 6.6 Hz, 6H), 1.46 – 1.32 (m, 6H), 0.96 – 0.88(t, J = 7.4 Hz, 9H). 13 C NMR (101 MHz, Chloroform-d) δ 13 C NMR (101 MHz, Chloroform-d) δ 67.85 (d, J = 6.0 Hz), 32.00, 18.68, 13.54. 31 P NMR (162 MHz, Chloroform-d) δ 68.01. Example 2 The method of this embodiment is basically the same as that of embodiment 1, except that acetonitrile is used as the solvent in this embodiment. The trivalent phosphorus compound as in embodiment 1 is synthesized under this solvent type, and the product yield is 82%.

[0028] Example 3 The method of this embodiment is basically the same as that of embodiment 1, except that in this embodiment, tetrahydrofuran is used as the solvent. The trivalent phosphorus compound as in embodiment 1 is synthesized under this solvent type, and the product yield is 90%.

[0029] Example 4 The method of this embodiment is basically the same as that of embodiment 1, except that in this embodiment, dichloromethane is used as the solvent. Under this solvent type, the trivalent phosphorus compound as in embodiment 1 is synthesized, and the product yield is 81%.

[0030] Example 5 The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite comprises the following steps:

[0031] In an argon atmosphere, 0.5 mmol tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, 7.5 mmol n-butanol, 0.3 mmol 4-methoxypyridine and 3 mL tetrahydrofuran (THF) were added to a Schlenk tube and mixed, and the mixture was stirred at room temperature for 2 h for nucleophilic reaction. After the reaction, the crude reaction solution was distilled under reduced pressure to remove tetrahydrofuran, and the target trivalent phosphorus compound was obtained after separation and purification by column chromatography, and the product yield was 78%.

[0032] Example 6 The method of this embodiment is basically the same as that of embodiment 5, except that in this embodiment, triethylamine is used as the alkaline agent. The trivalent phosphorus compound of embodiment 5 is synthesized under this solvent type, and the product yield is 50%.

[0033] Example 7 The method of this embodiment is basically the same as that of embodiment 5, except that in this embodiment, potassium carbonate is used as the alkaline agent. The trivalent phosphorus compound of embodiment 5 is synthesized under this solvent type, and the product yield is 83%.

[0034] Example 8 The method of this embodiment is basically the same as that of embodiment 5, except that in this embodiment, potassium tert-butoxide is used as the alkaline agent. The trivalent phosphorus compound of embodiment 5 is synthesized under this solvent type, and the product yield is 90%.

[0035] Example 9 The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite comprises the following steps:

[0036] In an argon atmosphere, 0.5 mmol tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, 7.5 mmol n-butanol, 0.3 mmol 4-dimethylaminopyridine and 3 mL tetrahydrofuran were added to a Schlenk tube and mixed. The mixture was stirred in an ice bath (0 °C) for 2 h for nucleophilic reaction. After the reaction, the obtained crude reaction solution was distilled under reduced pressure to remove tetrahydrofuran, and the target trivalent phosphorus compound was obtained after separation and purification by column chromatography. The product yield was 51%.

[0037] Example 10 The method of this example is basically the same as that of Example 9, except that in this example, the reaction temperature is 40° C. The trivalent phosphorus compound of Example 9 was synthesized under this solvent type, and the product yield was 91%.

[0038] Embodiment 11 The method of this embodiment is basically the same as that of embodiment 9, except that in this embodiment, the reaction temperature is 80° C. The trivalent phosphorus compound of embodiment 9 was synthesized under this solvent type, and the product yield was 91%.

[0039] Example 12 The method of this embodiment is basically the same as that of embodiment 9, except that in this embodiment, the reaction temperature is 120° C. The trivalent phosphorus compound of embodiment 9 is synthesized under this solvent type, and the product yield is 92%.

[0040] Embodiment 13 The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite comprises the following steps:

[0041] Under an argon atmosphere, 0.5 mmol of tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, 7.5 mmol of methanol, 0.3 mmol of 4-dimethylaminopyridine and 3 mL of tetrahydrofuran were added to a Schlenk tube and mixed, and the mixture was stirred at room temperature for 2 h for nucleophilic reaction. After the reaction, the obtained crude reaction solution was distilled under reduced pressure to remove tetrahydrofuran, and the target trivalent phosphorus compound was obtained after separation and purification by column chromatography, and the product yield was 93%.

[0042] Embodiment 14 The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite comprises the following steps:

[0043] Under an argon atmosphere, 0.5 mmol tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, 7.5 mmol ethanol, 0.3 mmol 4-dimethylaminopyridine and 3 mL tetrahydrofuran were added to a Schlenk tube and mixed, and the mixture was stirred at room temperature for 2 h for nucleophilic reaction. After the reaction, the obtained crude reaction solution was distilled under reduced pressure to remove tetrahydrofuran, and the target trivalent phosphorus compound was obtained after separation and purification by column chromatography, and the product yield was 93%.

[0044] Embodiment 15 The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite comprises the following steps:

[0045] Under an argon atmosphere, 0.5 mmol tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, 7.5 mmol 2-bromoethanol, 0.3 mmol 4-dimethylaminopyridine and 3 mL tetrahydrofuran were added to a Schlenk tube and mixed, and the mixture was stirred at room temperature for 2 h for nucleophilic reaction. After the reaction, the obtained crude reaction solution was distilled under reduced pressure to remove tetrahydrofuran, and the target trivalent phosphorus compound was obtained after separation and purification by column chromatography, and the product yield was 83%.

[0046] Example 16 In this example, trivalent phosphorus compounds were synthesized from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, and the applicability of synthesizing other types of phosphorus compounds by tautomerism was studied. The steps are as follows:

[0047] Under an argon atmosphere, 0.5 mmol of tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, 7.5 mmol of isopropanol, 0.3 mmol of 4-dimethylaminopyridine and 3 mL of tetrahydrofuran were added to a Schlenk tube and mixed. The mixture was stirred at room temperature for 2 h for nucleophilic reaction to generate the target trivalent phosphorus compound. Then, 0.2 mL of water was added and stirred for 30 min, and the trivalent phosphorus compound was tautomerized, so that hydrogen was isomerized from oxygen to phosphorus. Subsequently, tetrahydrofuran was removed by vacuum distillation, and the final product was obtained after separation and purification by column chromatography. The yield of the final product was 75%.

[0048] Embodiment 17 In this example, trivalent phosphorus compounds were synthesized from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, and the applicability of synthesizing other types of phosphorus compounds by tautomerism was studied. The steps are as follows:

[0049] Under argon atmosphere, 0.5 mmol tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, 7.5 mmol tert-butyl alcohol, 0.3 mmol 4-dimethylaminopyridine and 3 mL tetrahydrofuran were added to a Schlenk tube and mixed. The mixture was stirred at room temperature for 2 h for nucleophilic reaction to generate the target trivalent phosphorus compound. Then 0.2 mL of water was added and stirred for 30 min, and the trivalent phosphorus compound was tautomerized, so that hydrogen was isomerized from oxygen to phosphorus. Subsequently, tetrahydrofuran was removed by vacuum distillation, and the final product was obtained after separation and purification by column chromatography. The yield of the final product was 74%.

[0050] Embodiment 18 The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite comprises the following steps:

[0051] Under an argon atmosphere, 0.5 mmol tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, 7.5 mmol phenol, 0.3 mmol 4-dimethylaminopyridine and 3 mL tetrahydrofuran were added to a Schlenk tube and mixed, and the mixture was stirred at room temperature for 2 h for nucleophilic reaction. After the reaction, the obtained crude reaction solution was distilled under reduced pressure to remove tetrahydrofuran, and the target trivalent phosphorus compound was obtained after separation and purification by column chromatography, and the product yield was 90%.

[0052] 1 H NMR (400 MHz, Chloroform-d) δ 7.42 – 7.34 (m, 6H), 7.26 – 7.15 (m, 9H). 13 C NMR (101 MHz, Chloroform-d) δ 151.50 (d, J = 3.5 Hz), 129.66, 124.21 (d, J = 1.3 Hz), 120.66 (d, J = 7.0 Hz). 31 P NMR (162 MHz, Chloroform-d) δ127.89. Embodiment 19 The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite comprises the following steps:

[0053] At -78 °C, 0.5 mmol tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, 7.5 mmol allylmagnesium bromide, 0.3 mmol 4-dimethylaminopyridine and 3 mL tetrahydrofuran were added to a Schlenk tube under an argon atmosphere and mixed, and the mixture was stirred at room temperature for 2 h for nucleophilic reaction. After the reaction was completed, sulfur powder was also added to stabilize the reaction mixture and then separated. The obtained crude reaction solution was distilled under reduced pressure to remove tetrahydrofuran, and the target trivalent phosphorus compound was obtained after separation and purification by column chromatography, and the product yield was 98%.

[0054] 1 H NMR (400 MHz, Chloroform-d) δ 5.96 – 5.80 (ddtd, J = 17.5, 10.2,7.5, 5.4 Hz, 3H), 5.36 – 5.14 (m, 6H), 2.77 – 2.67 (ddt, J = 14.2, 7.5, 1.2Hz, 6H). 13 C NMR (101 MHz, Chloroform-d) δ 127.64 (d, J = 8.8 Hz), 121.01 (d, J = 12.3 Hz), 36.01 (d, J = 48.9 Hz). 31 P NMR (162 MHz, Chloroform-d) δ 42.52. Embodiment 20 The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite comprises the following steps:

[0055] At -78 °C, 0.5 mmol of tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, 7.5 mmol of phenyllithium, 0.3 mmol of 4-dimethylaminopyridine and 3 mL of tetrahydrofuran were added and mixed in a Schlenk tube under an argon atmosphere, and the mixture was stirred at room temperature for 2 h to perform a nucleophilic reaction. After the reaction, the obtained crude reaction solution was distilled under reduced pressure to remove tetrahydrofuran, and the target trivalent phosphorus compound was obtained after separation and purification by column chromatography, and the product yield was 99%.

[0056] Embodiment 21 The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite comprises the following steps:

[0057] Under argon atmosphere, 0.5 mmol tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, 7.5 mmol benzylamine, 0.3 mmol 4-dimethylaminopyridine and 3 mL tetrahydrofuran were added to a Schlenk tube and mixed, and the mixture was stirred at room temperature for 2 h for nucleophilic reaction. After the reaction, the obtained crude reaction solution was distilled under reduced pressure to remove tetrahydrofuran, and the target trivalent phosphorus compound was obtained after separation and purification by column chromatography, and the product yield was 85%.

[0058] Embodiment 22 The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite comprises the following steps:

[0059] Under argon atmosphere, 0.5 mmol tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, 7.5 mmol morpholine, 0.3 mmol 4-dimethylaminopyridine and 3 mL tetrahydrofuran were added to a Schlenk tube and mixed, and the mixture was stirred at room temperature for 2 h for nucleophilic reaction. After the reaction, the obtained crude reaction solution was distilled under reduced pressure to remove tetrahydrofuran, and the target trivalent phosphorus compound was obtained after separation and purification by column chromatography, and the product yield was 75%.

[0060] Embodiment 23 The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite comprises the following steps:

[0061] Under argon atmosphere, 0.5 mmol tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, 7.5 mmol aniline, 0.3 mmol 4-dimethylaminopyridine and 3 mL tetrahydrofuran were added to a Schlenk tube and mixed, and the mixture was stirred at room temperature for 2 h for nucleophilic reaction. After the reaction, the obtained crude reaction solution was distilled under reduced pressure to remove tetrahydrofuran, and the target trivalent phosphorus compound was obtained after separation and purification by column chromatography, and the product yield was 78%.

[0062] Embodiment 24 The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite comprises the following steps:

[0063] Under argon atmosphere, 0.5 mmol tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, 0.25 mmol pentaerythritol, 0.3 mmol 4-dimethylaminopyridine and 3 mL tetrahydrofuran were added to a Schlenk tube and mixed. The mixture was first stirred at 80 °C for 2 h for nucleophilic reaction, and then 3 mmol 2,4-di-tert-butylphenol was added and the stirring reaction was continued for 12 h. After the reaction was completed, the obtained crude reaction solution was distilled under reduced pressure to remove tetrahydrofuran, and the target trivalent phosphorus compound was obtained after separation and purification by column chromatography, and the product yield was 35%.

[0064] Embodiment 25 The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite comprises the following steps:

[0065] Under argon atmosphere, 0.5 mmol tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, 0.5 mmol isopropanol, 0.3 mmol 4-dimethylaminopyridine and 3 mL tetrahydrofuran were added to a Schlenk tube and mixed. The mixture was first stirred at 40 °C for 2 h for nucleophilic reaction, and then 3 mmol 4-methylphenol was added and the stirring reaction was continued for 2 h. After the reaction was completed, the obtained crude reaction solution was distilled under reduced pressure to remove tetrahydrofuran, and the target trivalent phosphorus compound was obtained after separation and purification by column chromatography, and the product yield was 68%.

[0066] Embodiment 26 The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite comprises the following steps:

[0067] Under argon atmosphere, 0.5 mmol tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, 1 mmol phenylmagnesium bromide, 0.3 mmol 4-dimethylaminopyridine and 3 mL tetrahydrofuran were added to a Schlenk tube and mixed. The mixture was first stirred at 40 °C for 2 h for nucleophilic reaction, and then 3 mmol cyclohexylmagnesium bromide was added and the reaction was continued to be stirred for 2 h. After the reaction was completed, the obtained crude reaction solution was distilled under reduced pressure to remove tetrahydrofuran, and the target trivalent phosphorus compound was obtained after separation and purification by column chromatography, and the product yield was 48%.

[0068] Comparative Example 1 The method of this comparative example is basically the same as that of Example 1, except that in this example, cyclohexane is used as the type of solvent. The trivalent phosphorus compound as in Example 1 is synthesized under this type of solvent, but the product yield is only 34%. This comparative example shows that solvents of different polarities have a great influence on the degree of conversion of the reaction, and too low polarity is not conducive to the reaction.

[0069] Comparative Example 2 The method of this comparative example is basically the same as that of Example 5, except that in this example, the type of alkaline reagent is ammonia water (the amount of solute ammonia monohydrate is the same as that of the alkaline reagent in Example 5). The trivalent phosphorus compound of Example 5 was synthesized under this solvent type, but the product yield was only 10%. This is because there is water in ammonia water, which is easy to produce by-products, so the type of alkaline reagent needs to be reasonably selected during the reaction.

[0070] In summary, the method of the present invention has the advantages of wide substrate applicability, good selectivity, and high atomic utilization. In the pathway, tri(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite is used as a phosphorus transfer reagent to carry out nucleophilic reactions with a series of widely available nucleophilic reagents such as alcohols, phenols, amines, and organometallic reagents, and nucleophilic groups in the nucleophilic reagents are introduced into trivalent phosphorus to form various types of trivalent phosphorus compounds. No highly corrosive raw materials are used in the steps, and no violent redox reactions are involved. It also has the advantages of being mild, less polluting, and less corrosive to the device. There are few side reactions in the pathway, and the by-products are hexafluoroisopropanol compounds, which have good recycling value and meet the requirements of green synthesis. The present invention has good application prospects in the fields of functional materials and medicine.

[0071] The preferred specific embodiments of the present invention are described in detail above. It should be understood that a person skilled in the art can make many modifications and changes based on the concept of the present invention without creative work. Therefore, any technical solution that can be obtained by a person skilled in the art through logical analysis, reasoning or limited experiments based on the concept of the present invention on the basis of the prior art should be within the scope of protection determined by the claims.

Claims

1. A method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite, characterized in that: The steps include: tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite is used as a phosphorus transfer reagent, and is mixed with a nucleophilic reagent, an alkaline reagent, and an organic solvent under an inert atmosphere to carry out a nucleophilic reaction to obtain a crude reaction solution; the crude reaction solution is purified, and the product is collected to obtain a trivalent phosphorus compound; The nucleophilic reagent includes at least one of alcohol compounds and halides thereof, phenol compounds, amine compounds, and organic metal reagents.

2. The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite according to claim 1, characterized in that: The alcohol compound includes at least one of C1-C5 monohydric alcohol and polyhydric alcohol, the phenol compound includes at least one of phenol and its C1-C4 alkyl substituents, the amine compound includes at least one of aromatic primary amine and heterocyclic secondary amine, the organic metal reagent includes at least one of hydrocarbon metal reagent and aromatic metal reagent; the alkaline reagent includes at least one of an organic base and a salt that is ionized in a solution environment and is alkaline.

3. The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite according to claim 2, characterized in that: The alcohol compound includes at least one of methanol, ethanol, isopropanol, n-butanol, tert-butanol and pentaerythritol; the halogenated substance of the alcohol compound includes 2-bromoethanol.

4. The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite according to claim 2, characterized in that: The phenolic compound includes at least one of phenol, p-cresol and 2,4-di-tert-butylphenol.

5. The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite according to claim 2, characterized in that: The amine compound includes at least one of aniline, benzylamine and morpholine.

6. The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite according to claim 2, characterized in that: The organometallic reagent includes at least one of allylmagnesium bromide, phenylmagnesium bromide and cyclohexylmagnesium bromide.

7. The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite according to claim 2, characterized in that: The alkaline reagent includes at least one of 4-methoxypyridine, 4-methylpyridine, 4-dimethylaminopyridine, potassium tert-butoxide, triethylamine, potassium carbonate, and sodium carbonate.

8. The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite according to claim 1, characterized in that: The organic solvent includes at least one of dimethyl sulfoxide, acetonitrile, toluene, tetrahydrofuran, chloroform, dichloromethane and dichloroethane.

9. The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite according to claim 1, characterized in that: The amount of tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite added is 0.5 mmol; the amount of nucleophilic reagent added is 1-20 mmol; the amount of alkaline reagent added is 0.02-5 mmol; and the amount of organic solvent added is 1-10 mL.

10. The method for synthesizing a trivalent phosphorus compound from tris(1,1,1,3,3,3-hexafluoro-2-propyl)phosphite according to claim 1, characterized in that: The temperature of the nucleophilic reaction is 0-120°C, and the reaction time is 0.2-12 h.

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