A trialkyloxyphosphine compound derivative and a method for preparing the same

Abstract

The application provides a trialkyloxyphosphine compound derivative shown in formula (I) and a preparation method thereof. The trialkyloxyphosphine compound derivative is an organic phosphorus compound with a structure similar to that of trialkyloxyphosphine, which is directly synthesized by using white phosphorus. The process method avoids the use of highly polluting chlorine gas and subsequent emission problems in traditional phosphorus chemical production, and is a more environmentally friendly production method. In addition, the method disclosed by the application has simple steps, mild reaction conditions, simple post-treatment, and can obtain a yield of more than medium.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of organic phosphorus chemical industry, in particular to a trialkyl phosphine oxide derivative and a preparation method thereof. BACKGROUND

[0002] As a typical neutral extractant, trialkyl phosphine oxide is known to have good extraction effect on some rare noble metals, and has important application in the fields of hydrometallurgy and environmental science (see Non-Patent Literature 1). However, the alkyl chain of the trialkyl phosphine extractant molecule currently has no substituent group, so the range of polarity and steric hindrance control of the compound is limited, which affects the further improvement of its extraction effect (see Non-Patent Literature 1, Patent Literature 1). Therefore, synthesizing trialkyl phosphine oxide derivatives with substituents on the alkyl chain will be a very meaningful research direction to meet the practicality and diversity requirements of industry.

[0003] In traditional phosphorus chemical production, white phosphorus is the main phosphorus source for synthesizing organic phosphine compounds, and chlorine gas with high pollution will be used in the reaction process, which has great safety hazards (see Non-Patent Literature 2). Therefore, developing a chlorine-free method to directly synthesize organic phosphine compounds from white phosphorus has become a hot research topic (see Non-Patent Literature 3).

[0004] Therefore, the present application provides a method for directly synthesizing trialkyl phosphine derivatives from white phosphorus, which has the advantages of mild conditions and simple operation, and has important significance for the research and development of new extractants and environmental protection.

[0005] Prior art documents

[0006] Patent Literature:

[0007] Patent Literature 1: CN107445988A.

[0008] Non-Patent Literature:

[0009] Non-Patent Literature 1: Hydrometallurgy of China, 2010, 29, 233-237.

[0010] Non-Patent Literature 2: Chem. Rev., 2010, 110, 4164-4177.

[0011] Non-Patent Literature 3: Phosphorus Sulfur Silicon Relat. Elem., 2022, 197, 398-407. SUMMARY

[0012] Technical problems solved by the invention

[0013] The present invention is made in view of the above problems, and aims to provide a trialkyloxyphosphine compound derivative which can be synthesized efficiently by a simple reaction procedure using a simple and readily available chemical material, white phosphorus, and which can greatly reduce environmental pollution caused in the production process.

[0014] Solution to the problem

[0015] The technical solution of the present invention is as follows:

[0016] One solution of the present invention is a trialkyloxyphosphine compound derivative which is a trialkyloxyphosphine compound derivative represented by the following formula (I), characterized in that,

[0017]

[0018] In the formula, R is a phenyl group, a benzyl group, a thienyl group, a C1-C6 alkoxy group, a substituted or unsubstituted phenoxy group, or a substituted or unsubstituted benzyloxy group; and the substituents of the phenoxy group and the benzyloxy group are hydrogen, halogen, an alkyl group, or a trifluoromethyl group.

[0019] In one preferred embodiment, R is a phenyl group, a C1-C6 alkoxy group, a substituted or unsubstituted phenoxy group, or a substituted or unsubstituted benzyloxy group.

[0020] Another solution of the present invention is a method for producing a trialkyloxyphosphine compound derivative, which is a method for producing a trialkyloxyphosphine compound derivative represented by the following formula (I).

[0021]

[0022] The production method is as follows:

[0023] Into a reactor filled with nitrogen or argon, white phosphorus, a photocatalyst, an additive, a solvent, and a compound of formula (II) are sequentially added, mixed, and then irradiated with light, and stirred at room temperature for 12 hours or more, thereby producing a compound of formula (I).

[0024]

[0025] In the compound of formula (II), R is a phenyl group, a benzyl group, a thienyl group, a C1-C6 alkoxy group, a substituted or unsubstituted phenoxy group, or a substituted or unsubstituted benzyloxy group.

[0026] In one preferred embodiment, R is a phenyl group, a C1-C6 alkoxy group, a substituted or unsubstituted phenoxy group, or a substituted or unsubstituted benzyloxy group, and the substituents of the phenoxy group and the benzyloxy group are hydrogen, halogen, an alkyl group, or a trifluoromethyl group.

[0027] The light source used is visible light.

[0028] The photocatalyst used can be iridium tris(2-phenylpyridine) (abbreviated as Ir(ppy)3), 2,4,5,6-tetra(9-carbazolyl)-1,3-dicyanobenzene (abbreviated as 4CzIPN), tris(2,2'-bipyrazine) ruthenium di(hexafluorophosphate) (abbreviated as [Ru(bpz)3]PF6]2), bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)] iridium di(hexafluorophosphate) (abbreviated as {Ir[dF(CF3)ppy]2(dtbpy)}PF6), rhodamine 6G (abbreviated as Rhodamine 6G), or 10-methyl-9-mesityl acridine perchlorate (abbreviated as [Acr-Mes]ClO4).

[0029] The ratio of the photocatalyst to white phosphorus (calculated as phosphorus atoms) is in the range of 0.005 to 0.1 molar equivalents.

[0030] The additive used is an alkali metal compound, which is a hydroxide, carbonate, phosphate, acetate, or organic alcohol salt thereof, and an organic amine. The amount of the additive used is in the range of 1.0 to 5.0 molar equivalents relative to the amount of white phosphorus (calculated as phosphorus atoms).

[0031] As the solvent used in the above reaction, there is no particular limitation as long as it is an organic solvent that can dissolve the reactants and does not react with the α-halocarbonyl compound and white phosphorus. Examples include acetonitrile (MeCN), tetrahydrofuran (THF), ethyl acetate (EA), dichloromethane (DCM), toluene, acetone, ethylene glycol dimethyl ether (DME), and N,N-dimethylformamide (DMF).

[0032] The ratio of the compound of formula (II) to white phosphorus is in the range of 3.0 to 9.0 molar equivalents of the compound of formula (II) relative to white phosphorus (calculated as phosphorus atoms).

[0033] Effects of the Invention

[0034] According to the present application, a method for preparing a trialkyl phosphine oxide compound derivative is provided. The conventional synthesis method uses chlorine gas, which is highly polluting, and the reaction is also highly dangerous and the operation process is relatively complicated. In the reaction of the present application, white phosphorus (P4) and an α-bromocarbonyl compound are directly synthesized into a trialkyl phosphine oxide compound derivative under the action of visible light, thereby avoiding the use of chlorine gas, and there are no subsequent problems such as emission and post-treatment, and it is a more economical and environmentally friendly production method. In addition, it can be seen from the method disclosed in the present application that the raw materials of the present application are cheap and easy to obtain, the reaction conditions are mild, the post-treatment is simple, and a yield of more than medium can be obtained, so the reaction is economical and practical.

[0035] In addition, the trialkyloxyphosphine compound derivative provided by the present application can be used for the synthesis of drug molecules and liquid crystal materials, and can also be used for the research and development of new extractant molecules. Compared with the prior art, the present application can more conveniently modify the alkyl side chain substituent, thereby providing the possibility of further regulating the steric hindrance and polarity of the trialkyloxyphosphine compound derivative, and providing an excellent basis for further application of the trialkyloxyphosphine compound derivative. DETAILED DESCRIPTION

[0036] The above summary of the present application is further described in detail through specific examples, but this should not be understood as any limitation on the scope of protection of the present application. Any technical solution achieved based on the above summary of the present application belongs to the scope of the present application. The materials used in the test and the test method are generally and / or specifically described. Those skilled in the art will understand that, in the following, if not specifically stated, the room temperature described in the present application has the technical meaning known in the art, generally refers to 20-25℃; the chemicals are all from commercial sources.

[0037] The trialkyloxyphosphine compound derivative of the present application is a trialkyloxyphosphine compound derivative represented by formula (II).

[0038]

[0039] In the compound of formula (I), R is phenyl, benzyl, thienyl, C1-C6 alkoxy, substituted or unsubstituted phenoxy, or substituted or unsubstituted benzyloxy; the substituents on the phenoxy and benzyloxy are hydrogen, halogen, alkyl, trifluoromethyl. Among them, R is preferably phenyl, C1-C6 alkoxy, substituted or unsubstituted phenoxy, or substituted or unsubstituted benzyloxy; the C1-C6 alkoxy is preferably methoxy, ethoxy, n-propoxy, n-butoxy, t-butoxy, 2-methoxyethoxy; the substituents on the benzyloxy and phenoxy are preferably hydrogen, chlorine, methyl, trifluoromethyl.

[0040] Preparation of the compound

[0041] The preparation method of the trialkyloxyphosphine compound derivative of the present application is a preparation method of the trialkyloxyphosphine compound derivative represented by formula (I),

[0042] The preparation method is as follows:

[0043] Into a reactor filled with nitrogen or argon, white phosphorus, a photocatalyst, an additive, a solvent and a compound of formula (II) are sequentially added, mixed, irradiated, and stirred at room temperature for more than 12 hours, thereby preparing a compound of formula (I);

[0044]

[0045] In the compound of formula (I), R is phenyl, benzyl, thienyl, C1-C6 alkoxy, substituted or unsubstituted phenoxy, or substituted or unsubstituted benzyloxy; the substituents on the phenoxy and benzyloxy are hydrogen, halogen, alkyl, trifluoromethyl. Preferably, R is phenyl, C1-C6 alkoxy, substituted or unsubstituted phenoxy, or substituted or unsubstituted benzyloxy; the C1-C6 alkoxy is preferably methoxy, ethoxy, n-propoxy, n-butoxy, t-butoxy, 2-methoxyethoxy; the substituents on the benzyloxy and phenoxy are preferably hydrogen, chlorine, methyl, trifluoromethyl.

[0046] The light source used is visible light.

[0047] The ratio of the compound of formula (II) to white phosphorus is 3.0-9.0 times the molar equivalent, preferably 5.0-8.5 times the molar equivalent, more preferably 6.5-8.0 times the molar equivalent, of the compound of formula (II) to white phosphorus (calculated as phosphorus atoms) used.

[0048] The photocatalyst used can be iridium tris-2-phenylpyridine (abbreviated as Ir(ppy)3), 2,4,5,6-tetra(9-carbazolyl)-1,3-dicyanobenzene (abbreviated as 4CzIPN), tris(2,2'-bipyridine) ruthenium dichloride hexafluorophosphate (abbreviated as [Ru(bpz)3]PF6]2), bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bipyridine] iridium dichloride hexafluorophosphate (abbreviated as {Ir[dF(CF3)ppy]2(dtbpy)}PF6), Rhodamine 6G (abbreviated as Rhodamine 6G), or 10-methyl-9-mesityl acridine perchlorate (abbreviated as [Acr-Mes]ClO4), preferably iridium tris-2-phenylpyridine (abbreviated as Ir(ppy)3), bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bipyridine] iridium dichloride hexafluorophosphate (abbreviated as {Ir[dF(CF3)ppy]2(dtbpy)}PF6), or 2,4,5,6-tetra(9-carbazolyl)-1,3-dicyanobenzene (abbreviated as 4CzIPN), more preferably iridium tris-2-phenylpyridine (abbreviated as Ir(ppy)3).

[0049] The photocatalyst is used in a range of 0.005-0.1 times the molar amount, preferably 0.005-0.09 times the molar amount, more preferably 0.006-0.05 times the molar amount, relative to white phosphorus (calculated as phosphorus atoms).

[0050] The additive used is an alkali metal compound or an organic amine, the alkali metal compound being its hydroxide, carbonate, phosphate, acetate, organic alcoholate, the carbonate of the alkali metal being lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; the phosphate of the alkali metal being disodium hydrogen phosphate; the acetate of the alkali metal being sodium acetate; the organic alcoholate of the alkali metal being sodium ethoxide; the organic amine being triethylamine, 4-dimethylaminopyridine (abbreviated as DMAP), 1,4-diazabicyclo[2.2.2]octane (abbreviated as DABCO). The additive is preferably sodium acetate, sodium carbonate, cesium carbonate and sodium ethoxide, more preferably sodium acetate.

[0051] The additive is used in a range of 1.0 to 5.0 molar equivalents, preferably 1.0 to 3.0 molar equivalents, more preferably 1.5 to 2.5 molar equivalents, relative to white phosphorus (based on phosphorus atoms).

[0052] The reaction time in the method is 12 to 36 hours, preferably 18 to 30 hours, more preferably 20 to 24 hours, at room temperature.

[0053] As the solvent used in the above reaction, there is no particular limitation as long as an organic solvent in which the reactants are dissolved and which does not react with the α-halocarbonyl compound and white phosphorus. For example, acetonitrile (MeCN), tetrahydrofuran (THF), ethyl acetate (EA), dichloromethane (DCM), toluene, acetone, ethylene glycol dimethyl ether (DME) or N,N-dimethylformamide (DMF) and the like.

[0054] The above method for preparing the compound is specifically described below by way of examples.

[0055] 1. Synthesis of the compound of formula (I)

[0056] Example 1: Synthesis of [(2-ethoxy-2-oxovinyl)(2-methoxy-2-oxovinyl)(oxo-λ5-phosphanetriyl)ethyl] acetate (Triethyl 2,2',2"-(oxo-λ5-phosphanetriyl)triacetate)

[0057]

[0058] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), Ir(ppy)3(0.0075 mmol), NaOAc (0.45 mmol), THF (6.0 mL), ethyl bromoacetate (2.25 mmol) were sequentially placed into a 10 mL Schlenk tube with a stirrer. Stirring at room temperature, irradiation with a 10W 456 nm blue LED lamp for 24 h. After the reaction was completed, the reaction solution was concentrated, column chromatography was used to separate the product, and the product was obtained in 62% yield (yield calculation based on phosphorus atoms).

[0059] Main NMR data: 1 H NMR (500 MHz, CDC13) δ 1.30 (t, J = 7.1 Hz, 9H), 3.30 (d, J = 15.2 Hz, 6H), 4.22 (q, J = 7.1 Hz, 6H). 13 C NMR (126 MHz, CDC13) δ 14.2, 36.6 (d, J = 65.5 Hz), 62.1, 166.3 (d, J = 4.2 Hz). 31 P NMR (202 MHz, CDC13) δ 33.54 (s). HRMS (ESI) m / z: [M + H] + calcd for C 12 H 22 O7P + 309.1098; Found: 309.1097.

[0060] Example 2: Synthesis of { [bis(2-methoxy-2-oxoethyl)](oxo)-λ5- phosphoranetriyl} methyl acetate (Trimethyl 2,2',2"-(oxo-l5-phosphanetriyl)triacetate)

[0061]

[0062] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), Ir(ppy)3(0.0075 mmol), NaOAc (0.45 mmol), THF (6.0 mL), methyl bromoacetate (2.25 mmol) were sequentially placed into a 10 mL Schlenk tube with a stirrer. Stirring at room temperature, irradiation with a 10W 456 nm blue LED lamp for 24 h. After the reaction was completed, the reaction solution was concentrated, column chromatography was used to separate the product, and the product was obtained in 75% yield (yield calculation based on phosphorus atoms).

[0063] Main NMR data: 1H NMR (400 MHz, CDC13) δ 3.33 (d, J = 15.3 Hz, 6H), 3.77 (s, 9H). 13 CNMR (101 MHz, CDC13) δ 36.3 (d, J = 65.4 Hz), 52.9, 166.7 (d, J = 4.3 Hz). 31 P NMR (202 MHz, CDC13) δ 33.44 (s). HRMS (ESI) m / z: [M + H] + calcd for C9H 16 O7P + 267.0628; Found: 267.0633.

[0064] Example 3: Synthesis of (Oxido{bis[2-oxido-2-(propyloxy)ethyl]}-λ5- phosphanetriyl)triacetate

[0065]

[0066] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), Ir(ppy)3(0.0075 mmol), NaOAc (0.48 mmol), THF (6.0 mL), n-propyl bromoacetate (2.25 mmol) were sequentially placed in a 10 mL Schlenk tube with a stirrer. Stirring at room temperature, irradiation with a 10W 456 nm blue LED lamp for 24 h. After the reaction was completed, the reaction solution was concentrated, and column chromatography was used to separate the product to obtain the product in 52% yield (yield calculation based on phosphorus atoms).

[0067] Main NMR data: 1 H NMR (400 MHz, CDC13) δ 0.96 (t, J = 7.4 Hz, 9H), 1.69 (h, J = 7.1 Hz, 6H), 3.31 (d, J = 15.2 Hz, 6H), 4.11 (t, J = 6.8 Hz, 6H). 13 CNMR (101 MHz, CDC13) δ 10.4, 21.9, 36.6 (d, J = 65.5 Hz), 67.7, 166.4 (d, J = 4.3 Hz). 31 PNMR (243 MHz, CDC13) δ 33.45 (s). HRMS (ESI) m / z: [M + H] + calcd for C 15 H 28 O7P +351.1567; Found: 351.1567.

[0068] Example 4: Synthesis of tributyl 2,2',2"-(oxo-l5-phosphanetriyl)triacetate

[0069]

[0070] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), Ir(ppy)3(0.0080 mmol), NaOAc (0.45 mmol), THF (6.0 mL), n-butyl bromoacetate (2.25 mmol) were sequentially placed in a 10 mL Schlenk tube with a stirrer. Stirring at room temperature, irradiation with a 10W 456 nm blue LED lamp for 24 h. After the reaction was completed, the reaction solution was concentrated, column chromatography was used to separate the product, and the product was obtained in 52% yield (yield calculation based on phosphorus atoms).

[0071] Main NMR data: 1 H NMR (400 MHz, CDC13) δ 0.94 (t, J = 7.4 Hz, 9H), 1.39 (h, J = 7.4 Hz, 6H), 1.64 (p, J = 6.9 Hz, 6H), 3.31 (d, J = 15.2 Hz, 6H), 4.15 (t, J = 6.8 Hz, 6H). 13 C NMR (101 MHz, CDC13) δ 13.7, 19.1, 30.5, 36.5 (d, J = 65.6 Hz), 65.9, 166.3 (d, J = 4.2 Hz). 31 P NMR (202 MHz, CDC13) δ 33.44 (s). HRMS (ESI) m / z: [M + H] + calcd for C 18 H 34 O7P + 393.2037; Found: 393.2033.

[0072] Example 5: Synthesis of tri-tert-butyl 2,2',2"-(oxo-l5-phosphanetriyl)triacetate

[0073]

[0074] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), Ir(ppy)3(0.0075 mmol), NaOAc (0.45 mmol), THF (6.0 mL), tert-butyl bromoacetate (2.21 mmol) were sequentially placed into a 10 mL Schlenk tube with a stirrer. Stirring at room temperature, irradiation with a 10W 456 nm blue LED lamp for 24 h. After the reaction was completed, the reaction solution was concentrated, and column chromatography was used to separate the product, which was obtained in 21% yield (yield calculation based on phosphorus atoms).

[0075] Main NMR data: 1 H NMR (400 MHz, CDC13) δ 1.49 (s, 27H), 3.18 (d, J = 14.8 Hz, 6H). 13 CNMR (101 MHz, CDC13) δ 28.1, 37.7 (d, J = 65.1 Hz), 82.9, 165.4 (d, J = 4.4 Hz). 31 P NMR (243 MHz, CDC13) δ 33.74 (s). HRMS (ESI) m / z: [M + H] + calcd for C 18 H 34 O7P + 393.2037; Found: 393.2027.

[0076] Example 6: Synthesis of {oxido[bis(6-oxido-2,5-dioxopentyl)]-l5- phosphanyl}acetic acid-2-methoxyethyl ester (Tris(2-methoxyethyl) 2,2',2"-(oxo- l5-phosphanetriyl)triacetate)

[0077]

[0078] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), Ir(ppy)3(0.0075 mmol), NaOAc (0.45 mmol), THF (6.0 mL), 2-methoxyethyl bromoacetate (2.25 mmol) were sequentially placed into a 10 mL Schlenk tube with a stirrer. Stirring at room temperature, irradiation with a 10W 456 nm blue LED lamp for 22 h. After the reaction was completed, the reaction solution was concentrated, and column chromatography was used to separate the product, which was obtained in 43% yield (yield calculation based on phosphorus atoms).

[0079] Main NMR data: 1H NMR (400 MHz, CDC13) δ 3.31 - 3.46 (m, 15H), 3.61 (t, J = 3.4 Hz, 6H), 4.31 (t, J = 3.3 Hz, 6H). 13 C NMR (101 MHz, CDC13) δ 36.5 (d, J = 64.8 Hz), 58.9, 64.7, 70.1, 166.1 (d, J = 4.4 Hz). 31 P NMR (243 MHz, CDC13) δ 33.30 (s). HRMS (ESI) m / z: [M + H] + calcd for C 15 H 28 O 10 P + 399.1415; Found: 399.1414.

[0080] Example 7: Synthesis of 2-{oxyl[bi s(2-oxyl-2-phenylethyl)]-λ5- phosphoranetriyl}-l-phenylethan-l-one (2,2',2"-(oxo-15-phosphanetriyl)tris(l- phenylethan-l-one)

[0081]

[0082] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), Ir(ppy)3(0.0075 mmol), NaOAc (0.45 mmol), THF (6.0 mL), 2-bromoacetophenone (2.25 mmol) were sequentially placed in a 10 mL Schlenk tube with a stirrer. Stirring at room temperature, irradiation with a 10W 456 nm blue LED lamp for 24 h. After the reaction was completed, the reaction solution was concentrated, and column chromatography was used to separate the product to obtain the product in 27% yield (yield calculation based on phosphorus atoms).

[0083] Main NMR data: 1 H NMR (400 MHz, CDC13) δ 4.07 (d, J = 15.3 Hz, 6H), 7.48 (t, J = 7.7 Hz, 6H), 7.56 - 7.71 (m, 3H), 7.92 - 8.15 (m, 6H). 13 C NMR (101 MHz, CDC13) δ 40.4 (d, J = 64.7 Hz), 128.9, 128.9, 134.1, 137.0, 194.2 (d, J = 6.0 Hz). 31 P NMR (243 MHz, CDC13) δ 36.38 (s). HRMS (ESI) m / z: [M + H]+ calcd for C 24 H 22 O4P + 405.1250; Found: 405.1247.

[0084] Example 8: Tribenzyl 2,2',2"-(oxo-l5-phosphanetriyl)triacetate

[0085]

[0086] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), Ir(ppy)3(0.0075 mmol), NaOAc (0.45 mmol), THF (6.0 mL), benzyl bromoacetate (2.30 mmol) were sequentially placed into a 10 mL Schlenk tube with a stirrer. Stirring at room temperature, irradiation with a 10W 456 nm blue LED lamp for 24 h. After the reaction was completed, the reaction solution was concentrated, column chromatography was used to separate the product, and the yield was 53% (yield calculation was based on phosphorus atom).

[0087] Main NMR data: 1 H NMR (400 MHz, CDC13) δ 3.29 (d, J = 15.1 Hz, 6H), 5.13 (s, 6H), 7.28-7.39 (m, 15H). 13 C NMR (101 MHz, CDC13) δ 36.6 (d, J = 65.2 Hz), 67.8, 128.6, 128.7, 128.8, 135.0, 166.0 (d, J = 4.2 Hz). 31 P NMR (243 MHz, CDC13) δ 33.15 (s). HRMS (ESI) m / z: [M + H] + calcd for C 27 H 28 O7P + 495.1567; Found: 495.1566.

[0088] Example 9: Tris(4-methylbenzyl) 2,2',2"-(oxo-l5-phosphanetriyl)triacetate

[0089]

[0090] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), Ir(ppy)3(0.0075 mmol), NaOAc (0.45 mmol), THF (6.0 mL), bromoacetic acid-(4-methylphenyl)methyl ester (2.25 mmol) were sequentially placed into a 10 mL Schlenk tube with a stirrer. Stirring at room temperature, irradiation with a 10W 456 nm blue LED lamp for 24 h. After the reaction was completed, the reaction solution was concentrated, column chromatography was separated to obtain the product in 47% yield (yield calculation based on phosphorus atom).

[0091] Main NMR data: 1 H NMR (400 MHz, CDC13) δ 2.33 (s, 9H), 3.26 (d, J = 15.1 Hz, 6H), 5.08 (s, 6H), 7.14 (d, J = 7.7 Hz, 6H), 7.22 (d, J = 7.9 Hz, 6H). 13 C NMR (101 MHz, CDC13) δ 21.2, 36.5 (d, J = 65.1 Hz), 67.6, 128.6, 129.3, 131.9, 138.5, 166.0 (d, J = 4.3 Hz). 31 P NMR (243 MHz, CDC13) δ 32.89 (s). HRMS (ESI) m / z: [M + H] + calcd for C 30 H 34 O7P + 537.2037; Found: 537.2029.

[0092] Example 10: (Oxido{bis[2-oxido-2-({[4-(trifluoromethyl)phenyl]methyl}oxy)ethyl]}- l5-methanephosphanoato)acetic acid-[4-(trifluoromethyl)phenyl] methyl ester (tris(4-(trifluoromethyl)benzyl) 2,2',2"-(oxo-l5-phosphanetriyl)triacetate)

[0093]

[0094] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), Ir(ppy)3(0.0075 mmol), NaOAc (0.45 mmol), THF (6.0 mL), bromoacetic acid-[4- (trifluoromethyl)phenyl]methyl ester (2.25 mmol) were added into a 10 mL Schlenk tube with a stirrer in sequence. Stirring at room temperature, irradiation with a 10W 456 nm blue LED lamp for 24 h. After the reaction was completed, the reaction solution was concentrated, and column chromatography was used for separation to obtain the product in 32% yield (yield calculation based on phosphorus atom).

[0095] Main NMR data: 1 H NMR (400 MHz, CDC13) δ 3.36 (d, J = 15.1 Hz, 6H), 5.20 (s, 6H), 7.46 (d, J = 8.0 Hz, 6H), 7.60 (d, J = 8.0 Hz, 6H). 13 C NMR (101 MHz, CDC13) δ 36.4 (d, J = 65.3 Hz), 66.8, 124.0 (q, J = 272.1 Hz), 125.7 (q, J = 3.7 Hz), 128.4, 130.8 (q, J = 32.6 Hz), 138.9, 166.0 (d, J = 4.2 Hz). 31 P NMR (243 MHz, CDC13) δ 33.06 (s). HRMS (ESI) m / z: [M + H] + calcd for C 30 H 25 F9O7P + 699.1189; Found: 699.1189.

[0096] Example 11: Synthesis of {[bis(2-{[(4-chlorophenyl)methyl]oxy}-2-oxovinyl) (oxo- 15-phosphanetriyl)]-λ5-methanephosphonate} (4-chlorophenyl)methyl ester (Tris(4-chlorobenzyl) 2,2',2"-(oxo-l5-phosphanetriyl)triacetate)

[0097]

[0098] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), Ir(ppy)3(0.0075 mmol), NaOAc (0.45 mmol), THF (6.0 mL), bromoacetic acid-(4- chlorophenyl)methyl ester (2.25 mmol) were sequentially added into a 10 mL Schlenk tube with a stirrer. Stirring at room temperature, irradiation with a 10W 456 nm blue LED lamp for 24 h. After the reaction was completed, the reaction solution was concentrated, and column chromatography was used for separation to obtain the product in 23% yield (yield calculation based on phosphorus atoms).

[0099] Main NMR data: 1 H NMR (400 MHz, CDC13) δ 3.28 (d, J = 15.1 Hz, 6H), 5.10 (s, 6H), 7.19 - 7.46 (m, 12H). 13 C NMR (101 MHz, CDC13) δ 36.5 (d, J = 65.1 Hz), 67.0, 129.0, 129.9, 133.5, 134.7, 166.0 (d, J = 4.2 Hz). 31 P NMR (243 MHz, CDC13) δ 33.06 (s). HRMS (ESI) m / z: [M + H] + calcd for C 27 H 25 Cl3O7P + 597.0398; Found: 597.0389.

[0100] Example 12: Synthesis of triphenyl 2,2',2"-(oxo-l5-phosphanetriyl)triacetate

[0101]

[0102] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), Ir(ppy)3(0.0075 mmol), NaOAc (0.45 mmol), THF (6.0 mL), bromoacetic acid-(4- chlorophenyl)methyl ester (2.25 mmol) were sequentially added into a 10 mL Schlenk tube with a stirrer. Stirring at room temperature, irradiation with a 10W 456 nm blue LED lamp for 24 h. After the reaction was completed, the reaction solution was concentrated, and column chromatography was used for separation to obtain the product in 23% yield (yield calculation based on phosphorus atoms).

[0103] Main NMR data: 1H NMR (400 MHz, CDC13) δ 3.70 (d, J = 15.2 Hz, 6H), 7.12 (dd, J = 7.5, 1.6 Hz, 6H), 7.20 - 7.31 (m, 3H), 7.37 (t, J = 7.8 Hz, 6H). 13 C NMR (101 MHz, CDC13) δ 36.8 (d, J = 65.8 Hz), 121.5, 126.6, 129.7, 150.3, 165.2 (d, J = 4.1 Hz). 31 P NMR (243 MHz, CDC13) δ 33.36 (s). HRMS (ESI) m / z: [M + H] + calcd for C 24 H 22 O7P + 453.1098; Found: 453.1092.

[0104] Example 13: Synthesis of [(bis{2-[(4-methylphenyl)oxy]-2-oxovinyl} (oxo-λ5- phosphanyl)ethyl] acetate-4-methylphenyl ester (tri-p-tolyl 2,2',2"-(oxo-15- phosphanetriyl)triacetate)

[0105]

[0106] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), Ir(ppy)3(0.0075 mmol), NaOAc (0.45 mmol), THF (6.0 mL), bromoacetic acid-4-methylphenyl ester (2.25 mmol) were sequentially placed in a 10 mL Schlenk tube with a stirrer. Stirring at room temperature, irradiation with a 10W 456 nm blue LED lamp for 24 h. After the reaction was completed, the reaction solution was concentrated, and column chromatography was used to separate the product to obtain the product in 40% yield (yield calculation based on phosphorus atoms).

[0107] Main NMR data: 1 H NMR (400 MHz, CDC13) δ 2.34 (s, 9H), 3.66 (d, J = 15.1 Hz, 6H), 7.00 (d, J = 8.4 Hz, 6H), 7.16 (d, J = 8.2 Hz, 6H). 13 C NMR (101 MHz, CDC13) δ 21.0, 36.7 (d, J = 65.7 Hz), 121.2, 130.2, 136.3, 148.1, 165.4 (d, J = 4.1 Hz). 31PNMR (243 MHz, CDC13) δ 33.49 (s). HRMS (ESI) m / z: [M+H] + calcd for C 27 H 28 O7P + 495.1567; Found: 495.1567.

[0108] availability of the industry

[0109] The synthesized phosphorus compounds have broad application prospects in the synthesis of organic ligands and the extraction of rare and precious metals.

Claims

1. A method for producing a trialkyloxyphosphine derivative, which is a method for producing a trialkyloxyphosphine derivative of the following formula (I), ###0001### wherein R is a phenyl group, a C1-C6 alkoxy group, a substituted or unsubstituted phenoxy group, or a substituted or unsubstituted benzyloxy group; and the substituents of the phenoxy group and the benzyloxy group are hydrogen, chlorine, a methyl group, or a trifluoromethyl group. wherein The method is as follows: a reactor filled with nitrogen or argon is charged with white phosphorus, a photo-catalyst, an additive, a solvent, and a compound of the following formula (II), ###0002### and the mixture is irradiated with light and stirred at room temperature for 12 hours or more, thereby producing a compound of the formula (I). The amount of the compound of the formula (II) used is 3.0 to 9.0 times the molar equivalent of white phosphorus in terms of the phosphorus atom. In the above method, the light source is visible light. The photo-catalyst is iridium trisphenylpyridine, 2,4,5,6-tetra(9-carbazolyl)-1,3-dicyanobenzene, tris(2,2'-bipyridyl)ruthenium dichloride hexafluorophosphate, bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium dichloride hexafluorophosphate, rhodamine 6G, or 10-methyl-9-cymene acridinium perchlorate. The additive is an alkali metal compound or an organic amine, and the alkali metal compound is a hydroxide, a carbonate, a phosphate, an acetate, or an organic alcoholate thereof. In the above method, the reaction time is 12 to 36 hours. The photo-catalyst is used in a proportion of 0.005 to 0.1 times the molar equivalent of white phosphorus in terms of the phosphorus atom, and the additive is used in a proportion of 1.0 to 5.0 times the molar equivalent of white phosphorus in terms of the phosphorus atom.

2. The method of claim 1, wherein the trialkyl phosphine oxide derivative is prepared by the reaction of a compound of formula (II) with a compound of formula (III) in the presence of a base.

2. The method according to claim 1, wherein the light source is visible light.

3. The method for preparing the trialkylphosphine oxide derivative according to claim 1, characterized in that, 3. The method according to claim 1 or 2, wherein the photo-catalyst is iridium trisphenylpyridine, 2,4,5,6-tetra(9-carbazolyl)-1,3-dicyanobenzene, tris(2,2'-bipyridyl)ruthenium dichloride hexafluorophosphate, bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium dichloride hexafluorophosphate, rhodamine 6G, or 10-methyl-9-cymene acridinium perchlorate.

4. The method according to any one of claims 1 to 3, wherein the additive is an alkali metal compound or an organic amine, and the alkali metal compound is a hydroxide, a carbonate, a phosphate, an acetate, or an organic alcoholate thereof.

5. The method according to any one of claims 1 to 4, wherein the reaction time is 12 to 36 hours.

6. The method according to any one of claims 1 to 5, wherein the photo-catalyst is used in a proportion of 0.005 to 0.1 times the molar equivalent of white phosphorus in terms of the phosphorus atom, and the additive is used in a proportion of 1.0 to 5.0 times the molar equivalent of white phosphorus in terms of the phosphorus atom.

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