Novel organic phosphorus-fluorine compound and its synthesis method

Abstract

The present invention discloses a class of organophosphorus fluoride compounds and a synthesis method thereof. The method uses diphenyl(dialkyl)phosphine oxide compounds and trifluoromethyltrimethylsilane (TMSCF3) as the main raw materials, potassium carbonate as the base, sodium iodide and water as additives, tetrahydrofuran as the solvent, and under the condition of 150 °C in a nitrogen atmosphere, the organophosphorus fluoride compounds are efficiently synthesized. The method has the advantages of low cost, relatively high yield, simple operation, etc., and has potential industrial application prospects. Moreover, this class of compounds is also expected to be applied in organophosphorus ligands.

Description

[Technical field]

[0001] The invention belongs to the field of catalytic organic synthesis, and in particular relates to organic phosphorus-fluorine compounds and a synthesis method thereof. [Background technology]

[0002] As an important branch of organic chemistry, organophosphorus chemistry has always attracted extensive attention. In recent years, with the continuous development and application of organophosphorus ligands, organophosphorus pesticides and drugs, organophosphorus chemistry has become one of the research hotspots in the field of chemistry. As an important organic synthesis intermediate, diphenylphosphine oxide (DPO) plays an important role in the synthesis of various pesticides and chiral phosphine ligands.

[0003] There are few reported cases of fluorination of phosphine oxide compounds. Currently known cases include silicon trifluoromethylation and deoxygenation trifluoromethylation of phosphine oxide compounds. However, these reactions face the disadvantages of using dangerous fluorination reagents, poor substrate adaptability, and low yield. At present, no one has reported the deoxygenation difluoromethylation of phosphine oxide compounds. Therefore, we developed a method using diphenyl (dialkyl) phosphine oxide and TMSCF. 3 The invention discloses a method for the deoxygenation of diphenylphosphine oxide compounds, which does not use a transition metal catalyst, has simple and easy operation conditions, good substrate adaptability, and high yield. In addition, a new trivalent phosphorus compound is generated, which is expected to be applied to phosphorus ligands. At present, there are no public documents or patent applications for the deoxygenation of diphenylphosphine oxide compounds at home and abroad. [Summary of the invention]

[0004] The object of the present invention is to provide a method for preparing a novel nanostructured carbonyl phosphate nanoparticle by using diphenylphosphine oxide compounds and TMSCF under different conditions. 3 As raw materials, organic phosphorus and fluorine compounds can be efficiently synthesized. The method has the advantages of low cost, high yield, simple operation, no pollution, etc., and has certain feasibility for realizing its industrial production. In order to achieve the above invention purpose, the present invention proposes the following technical scheme:

[0005] In order to achieve the above-mentioned object of the invention, the present invention proposes the following technical solutions:

[0006] A class of organophosphorus compounds and a method for synthesizing the same, wherein the structural formulas of organophosphorus compounds I and II are as follows:

[0007]

[0008] Wherein the compound I comprises R 1is selected from 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-biphenyl, 4-nitrodimethylphenyl, 3-methylphenyl, 3-fluorophenyl, 2-methylphenyl, 3,5-dimethylphenyl, naphthyl, cyclopentyl, cyclohexyl, n-pentyl, n-hexyl, ethyl, isopropyl, tert-butyl; R 2 Selected from 2-methylphenyl; R 3 The catalytic synthesis method of compound I and II is characterized in that diphenyl (dialkyl) phosphorus oxide III, IV and trifluoromethyltrimethylsilane (TMSCF 3 )V as raw material, tetrahydrofuran as solvent, 1 equivalent of potassium carbonate as base, 1.5 equivalents of sodium iodide as additive, 1 equivalent of water, temperature of 150° C., reaction under nitrogen atmosphere for 12 hours to obtain organophosphorus compounds I and II.

[0009] In the above-mentioned synthesis method, the raw materials are diphenyl (dialkyl) phosphine oxide compounds III, IV and trifluoromethyltrimethylsilane (TMSCF 3 )V has the following structural formula:

[0010]

[0011] Wherein the III, IV compound includes R 1 is selected from 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-biphenyl, 4-nitrodimethylphenyl, 3-methylphenyl, 3-fluorophenyl, 2-methylphenyl, 3,5-dimethylphenyl, naphthyl, cyclopentyl, cyclohexyl, n-pentyl, n-hexyl, ethyl, isopropyl, tert-butyl; R 2 Selected from 2-methylphenyl; R 3 Selected from phenyl.

[0012] In the above-mentioned synthesis method, diphenyl (dialkyl) phosphorus oxide III, IV and trifluoromethyl trimethylsilane (TMSCF 3 )V as raw material, tetrahydrofuran as solvent, 1 equivalent of potassium carbonate as base, 1.5 equivalents of sodium iodide as additive, 1 equivalent of water, temperature of 150° C., and reaction for 12 hours under nitrogen atmosphere.

[0013] The invention provides a highly efficient synthesis method for a class of organic phosphorus-fluorine compounds, which opens up a new low-cost "green" approach, and has the advantages of: a wider source of diphenyl (dialkyl) phosphine oxides, cheap and readily available fluorination reagents, a higher yield of the target product, and simple reaction operations.

Brief Description of the Drawings

[0014] Attached Figure 1 Shown is a route map for preparing organic phosphorus fluoride compounds provided by the present invention. [Specific implementation method]

[0015] The present invention provides a highly efficient synthesis method of organic phosphorus fluoride compounds, see the attached Figure 1 :Diphenyl (dialkyl) phosphine oxide and trifluoromethyl trimethylsilane (TMSCF 3 ) as raw material, tetrahydrofuran as solvent, 1 equivalent of potassium carbonate as base, 1.5 equivalents of sodium iodide as additive, 1 equivalent of water, temperature of 150°C, reaction under nitrogen atmosphere for 12 hours, after completion of the reaction, column chromatography separation was used to obtain the target product.

[0016] The present invention will be further described below in conjunction with specific preparation examples:

[0017] Preparation Example 1

[0018] Add 0.3 mmol of diphenyl (dialkyl) phosphine oxide III into a 10 mL reaction tube, add trifluoromethyl trimethylsilane (TMSCF 3 )V 1.35mmol, potassium carbonate 0.3mmol, sodium iodide 0.45mmol, water 0.3mmol, tetrahydrofuran 2mL, under nitrogen atmosphere, 150℃ for 12h. After the reaction, the organic phosphorus fluoride compound (R 1 =4-fluorophenyl) to give a colorless liquid in 72% yield.

[0019] Preparation Example 2

[0020] Add 0.3 mmol of diphenyl (dialkyl) phosphine oxide III into a 10 mL reaction tube, add trifluoromethyl trimethylsilane (TMSCF 3 )V 1.35mmol, potassium carbonate 0.3mmol, sodium iodide 0.45mmol, water 0.3mmol, tetrahydrofuran 2mL, under nitrogen atmosphere, 150℃ for 12h. After the reaction, the organic phosphorus fluoride compound (R 1 =4-chlorophenyl) to give a colorless liquid in 70% yield.

[0021] Preparation Example 3

[0022] Add 0.3 mmol of diphenyl (dialkyl) phosphine oxide III into a 10 mL reaction tube, add trifluoromethyl trimethylsilane (TMSCF 3 )V 1.35mmol, potassium carbonate 0.3mmol, sodium iodide 0.45mmol, water 0.3mmol, tetrahydrofuran 2mL, under nitrogen atmosphere, 150℃ for 12h. After the reaction, the organic phosphorus fluoride compound (R 1 =4-bromophenyl) to give a colorless liquid in 75% yield.

[0023] Preparation Example 4

[0024] Add 0.3 mmol of diphenyl (dialkyl) phosphine oxide III into a 10 mL reaction tube, add trifluoromethyl trimethylsilane (TMSCF 3 )V 1.35mmol, potassium carbonate 0.3mmol, sodium iodide 0.45mmol, water 0.3mmol, tetrahydrofuran 2mL, under nitrogen atmosphere, 150℃ for 12h. After the reaction, the organic phosphorus fluoride compound (R 1 =4-biphenyl) to give a colorless liquid in 52% yield.

[0025] Preparation Example 5

[0026] Add 0.3 mmol of diphenyl (dialkyl) phosphine oxide III into a 10 mL reaction tube, add trifluoromethyl trimethylsilane (TMSCF 3 )V 1.35mmol, potassium carbonate 0.3mmol, sodium iodide 0.45mmol, water 0.3mmol, tetrahydrofuran 2mL, under nitrogen atmosphere, 150℃ for 12h. After the reaction, the organic phosphorus fluoride compound (R 1 =4-nitrogen dimethylphenyl) to give a yellow solid with a yield of 86%.

[0027] Preparation Example 6

[0028] Add 0.3 mmol of diphenyl (dialkyl) phosphine oxide III into a 10 mL reaction tube, add trifluoromethyl trimethylsilane (TMSCF 3 )V 1.35mmol, potassium carbonate 0.3mmol, sodium iodide 0.45mmol, water 0.3mmol, tetrahydrofuran 2mL, under nitrogen atmosphere, 150℃ for 12h. After the reaction, the organic phosphorus fluoride compound (R 1 =3-methylphenyl) to give a colorless liquid in 82% yield.

[0029] Preparation Example 7

[0030] Add 0.3 mmol of diphenyl (dialkyl) phosphine oxide III into a 10 mL reaction tube, add trifluoromethyl trimethylsilane (TMSCF 3 )V 1.35mmol, potassium carbonate 0.3mmol, sodium iodide 0.45mmol, water 0.3mmol, tetrahydrofuran 2mL, under nitrogen atmosphere, 150℃ for 12h. After the reaction, the organic phosphorus fluoride compound (R 1 =3-fluorophenyl) to give a colorless liquid in 74% yield.

[0031] Preparation Example 8

[0032] Add 0.3 mmol of diphenyl (dialkyl) phosphine oxide III into a 10 mL reaction tube, add trifluoromethyl trimethylsilane (TMSCF 3 )V 1.35mmol, potassium carbonate 0.3mmol, sodium iodide 0.45mmol, water 0.3mmol, tetrahydrofuran 2mL, under nitrogen atmosphere, 150℃ for 12h. After the reaction, the organic phosphorus fluoride compound (R 1 =4-biphenyl) to give a yellow solid in 52% yield.

[0033] Preparation Example 9

[0034] Add 0.3 mmol of diphenyl (dialkyl) phosphine oxide III into a 10 mL reaction tube, add trifluoromethyl trimethylsilane (TMSCF 3 )V 1.35mmol, potassium carbonate 0.3mmol, sodium iodide 0.45mmol, water 0.3mmol, tetrahydrofuran 2mL, under nitrogen atmosphere, 150℃ for 12h. After the reaction, the organic phosphorus fluoride compound (R 1 =2-methylphenyl) to give a yellow solid in 76% yield.

[0035] Preparation Example 10

[0036] Add 0.3 mmol of diphenyl (dialkyl) phosphine oxide III into a 10 mL reaction tube, add trifluoromethyl trimethylsilane (TMSCF 3 )V 1.35mmol, potassium carbonate 0.3mmol, sodium iodide 0.45mmol, water 0.3mmol, tetrahydrofuran 2mL, under nitrogen atmosphere, 150℃ for 12h. After the reaction, the organic phosphorus fluoride compound (R 1 =3,5-dimethylphenyl) to give a colorless liquid with a yield of 80%.

[0037] Preparation Example 11

[0038] Add 0.3 mmol of diphenyl (dialkyl) phosphine oxide III into a 10 mL reaction tube, add trifluoromethyl trimethylsilane (TMSCF 3 )V 1.35mmol, potassium carbonate 0.3mmol, sodium iodide 0.45mmol, water 0.3mmol, tetrahydrofuran 2mL, under nitrogen atmosphere, 150℃ for 12h. After the reaction, the organic phosphorus fluoride compound (R 1=naphthyl) to give a white solid in 62% yield.

[0039] Preparation Example 12

[0040] Add 0.3 mmol of diphenyl (dialkyl) phosphine oxide III into a 10 mL reaction tube, add trifluoromethyl trimethylsilane (TMSCF 3 )V 1.35mmol, potassium carbonate 0.3mmol, sodium iodide 0.45mmol, water 0.3mmol, tetrahydrofuran 2mL, under nitrogen atmosphere, 150℃ for 12h. After the reaction, the organic phosphorus fluoride compound (R 1 =cyclopentyl) to give a colorless liquid in 72% yield.

[0041] Preparation Example 13

[0042] Add 0.3 mmol of diphenyl (dialkyl) phosphine oxide III into a 10 mL reaction tube, add trifluoromethyl trimethylsilane (TMSCF 3 )V 1.35mmol, potassium carbonate 0.3mmol, sodium iodide 0.45mmol, water 0.3mmol, tetrahydrofuran 2mL, under nitrogen atmosphere, 150℃ for 12h. After the reaction, the organic phosphorus fluoride compound (R 1 =cyclohexyl) to give a colorless liquid in 76% yield.

[0043] Preparation Example 14

[0044] Add 0.3 mmol of diphenyl (dialkyl) phosphine oxide III into a 10 mL reaction tube, add trifluoromethyl trimethylsilane (TMSCF 3 )V 1.35mmol, potassium carbonate 0.3mmol, sodium iodide 0.45mmol, water 0.3mmol, tetrahydrofuran 2mL, under nitrogen atmosphere, 150℃ for 12h. After the reaction, the organic phosphorus fluoride compound (R 1 =n-pentyl) to give a colorless liquid in 72% yield.

[0045] Preparation Example 15

[0046] Add 0.3 mmol of diphenyl (dialkyl) phosphine oxide III into a 10 mL reaction tube, add trifluoromethyl trimethylsilane (TMSCF 3 )V 1.35mmol, potassium carbonate 0.3mmol, sodium iodide 0.45mmol, water 0.3mmol, tetrahydrofuran 2mL, under nitrogen atmosphere, 150℃ for 12h. After the reaction, the organic phosphorus fluoride compound (R1 =n-pentyl) to give a colorless liquid in 75% yield.

[0047] Preparation Example 16

[0048] Add 0.3 mmol of diphenyl (dialkyl) phosphine oxide III into a 10 mL reaction tube, add trifluoromethyl trimethylsilane (TMSCF 3 )V 1.35mmol, potassium carbonate 0.3mmol, sodium iodide 0.45mmol, water 0.3mmol, tetrahydrofuran 2mL, under nitrogen atmosphere, 150℃ for 12h. After the reaction, the organic phosphorus fluoride compound (R 1 =ethyl) to give a colorless liquid with a yield of 82%.

[0049] Preparation Example 17

[0050] Add 0.3 mmol of diphenyl (dialkyl) phosphine oxide III into a 10 mL reaction tube, add trifluoromethyl trimethylsilane (TMSCF 3 )V 1.35mmol, potassium carbonate 0.3mmol, sodium iodide 0.45mmol, water 0.3mmol, tetrahydrofuran 2mL, under nitrogen atmosphere, 150℃ for 12h. After the reaction, the organic phosphorus fluoride compound (R 1 =isopropyl) to give a colorless liquid in 85% yield.

[0051] Preparation Example 18

[0052] Add 0.3 mmol of diphenyl (dialkyl) phosphine oxide III into a 10 mL reaction tube, add trifluoromethyl trimethylsilane (TMSCF 3 )V 1.35mmol, potassium carbonate 0.3mmol, sodium iodide 0.45mmol, water 0.3mmol, tetrahydrofuran 2mL, under nitrogen atmosphere, 150℃ for 12h. After the reaction, the organic phosphorus fluoride compound (R 1 =tert-butyl) to give a colorless liquid in 75% yield.

[0053] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be based on the attached claims.

Claims

1. A method for synthesizing an organic phosphorus-fluorine compound I, It is characterized in that The steps include: Compound III and 4.5 equivalents of trifluoromethyltrimethylsilane V are used as raw materials, tetrahydrofuran is used as solvent, 1 equivalent of potassium carbonate is used as a base, 1.5 equivalents of sodium iodide is used as an additive, 1 equivalent of water is used, the temperature is 150° C., and the reaction is carried out under a nitrogen atmosphere for 12 h to obtain an organic phosphorus fluoride compound I; Wherein, the structural formula of compound III is as follows: , the structural formula of trifluoromethyltrimethylsilane V is as follows: , the structural formula of the organic phosphorus fluoride compound I is as follows: , wherein R in the organic phosphorus fluoride compound I and compound III 1 Selected from 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-biphenyl, 3-methylphenyl, 3-fluorophenyl, 2-methylphenyl, 3,5-dimethylphenyl, naphthyl, cyclopentyl, cyclohexyl, n-pentyl, ethyl, isopropyl and tert-butyl.

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