Method for preparing 4-(2, 2-diaryl vinyl) thiobutyl phosphonate / phosphonate

Abstract

The invention provides a method for preparing 4-(2, 2-diaryl vinyl) thiobutyl phosphate / phosphonate, which is characterized in that cuprous iodide is used as a catalyst, 1-vinyl-tetrahydro-1H-thiophene-1-onium trifluoromethanesulfonate and an organic phosphoric acid compound are used as reaction substrates, and an organic solvent and alkali are added into a reaction system. The method has the advantages that the catalyst is cheap and easily available; the substrate applicability is high; reaction conditions are mild, safe and reliable; the selectivity of the obtained target product is close to 100%, and the yield is high.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalytic synthesis of organophosphorus / phosphonate compounds, and specifically relates to a method for efficiently preparing 4-(2,2-diarylvinyl)thiobutyl phosphorus / phosphonate by phosphoroxylation reaction of 1-vinyl-tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate and organic phosphoric acid.

Background Art

[0002] Organophosphorus / phosphonate compounds are an important class of organic synthesis intermediates. Especially, organophosphorus compounds containing a sulfur heteroatom substitution in the molecule have wide applications in pesticides, insecticides, pharmaceutical intermediates, biological agents, flame retardant materials, optoelectronic materials, and organic synthesis due to the special properties of their phosphoryl groups and sulfur atoms. In addition, during the post-functionalization reaction process of such compounds, the sulfur atom can further be converted into corresponding phosphoryl group-substituted sulfoxide and sulfone compounds under the action of an oxidant.

[0003] Currently, the methods reported in the literature for synthesizing organophosphorus compounds containing a sulfur heteroatom substitution in the molecule mainly include: (1) Nucleophilic substitution reaction: Using phosphoryl group-substituted alkyl halides and thiol or thiophenol compounds to undergo nucleophilic substitution reaction under the catalytic action of transition metals (such as copper, palladium, nickel, etc.) and bases. However, the above reactions have defects such as poor reaction selectivity, strong toxicity, and high cost. Moreover, the reaction reagents have a foul smell, poor functional group tolerance, and the reaction waste liquid is toxic, often requiring special treatment; (2) On-line activation reaction of sulfur powder: Using phosphoryl group-substituted alkyl halides / diazo compounds and sulfur powder and alkyl / aryl boronic acid and other compounds to construct corresponding C-S-C bond compounds by on-line activation of sulfur powder under the synergistic catalysis of transition metals (such as nickel, palladium, rhodium, etc.) and organic ligands with the strategy of reductive cross-coupling reaction. However, the above methods generally use environmentally unfriendly reagents (such as diazonium salts, halides, etc.), special ligands (such as phosphine-based, carbene-based ligands, etc.), and also have defects such as cumbersome experimental procedures, expensive catalysts that are difficult to recycle, harsh reaction conditions, cross-substrate applicability, low selectivity and yield, and large environmental pollution.

[0004] So far, there are several problems in the efficient synthesis of 4-(2,2-diarylvinyl)thiobutyl phosphorus / phosphonate compounds, such as the quality of raw materials, production safety (the foul smell and toxicity of thiol / phenol), and the stability and purity of products. The synthesis technology is difficult. Currently, only a few companies in the United States, Germany, etc. are producing, and most of the products of 4-(2,2-diarylvinyl)thiobutyl phosphorus / phosphonate compounds with special functional groups in our country mainly rely on imports at present.

[0005] In view of the deficiencies of the existing synthesis processes, the industry is focusing on developing a new method for efficiently catalyzing the synthesis of corresponding 4-(2,2-diarylvinyl)thiobutyl phosphates / phosphonates from stable, inexpensive and readily available raw materials using inexpensive catalysts.

Summary of the Invention

[0006] The object of the present invention is to provide a new method for efficiently and highly selectively synthesizing corresponding 4-(2,2-diarylvinyl)thiobutyl phosphates / phosphonates from inexpensive and readily available 1-vinyl-tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate and organic phosphoric acid compounds, so as to overcome the above defects in the prior art.

[0007] To achieve the above technical object, the present invention adopts the following technical solutions:

[0008] A method for preparing 4-(2,2-diarylvinyl)thiobutyl phosphates / phosphonates, wherein 1-vinyl-tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, organic phosphoric acid compounds, a catalyst, a base and an organic solvent are placed in a reaction vessel in an air environment for mixing, and reacted at 25-120 °C for 3-6 hours with stirring to obtain 4-(2,2-diarylvinyl)thiobutyl phosphates / phosphonates. The specific reaction formula is shown in formula (I):

[0009]

[0010] Among them, the catalyst is copper(I) iodide, the base is cesium carbonate, and the organic solvent is ethyl acetate;

[0011] R 1 is selected from one of phenyl, 4-methoxyphenyl, 4-methylphenyl, 4-fluorophenyl, 4-chlorophenyl, hydrogen atom, methyl;

[0012] R 2 is selected from one of phenyl, 4-methoxyphenyl, 4-methylphenyl, 4-fluorophenyl, 4-chlorophenyl, 2-methylphenyl, 2-fluorophenyl, 2-chlorophenyl, 3-bromophenyl, 4-phenylphenyl, 4-trifluoromethylphenyl, 3-chlorophenyl, 2-bromophenyl;

[0013] R 3 is selected from one of phenyl, 3-methylphenyl, 4-methylphenyl, 4-methoxyphenyl, 3,5-dimethylphenyl, 1-naphthyl, 2-naphthyl, cyclohexyl, phenoxy, benzyloxy, ethoxy, butoxy, 2-ethylhexoxy, tert-butoxy;

[0014] R 4Selected from phenyl, 3-methylphenyl, 4-methylphenyl, 4-methoxyphenyl, 3,5-dimethylphenyl, 1-naphthyl, 2-naphthyl, cyclohexyl, phenoxy, benzyloxy, ethoxy, butoxy, 2-ethylhexoxy, 2-ethylhexyl, tert-butoxy, methyl.

[0015] In the above method for synthesizing 4-(2,2-diarylethynyl)thiobutyl phosphoric / phosphonic acid esters from 1-vinyl-tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate and organic phosphoric acid compounds, 1-vinyl-tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate is selected from 1-(2,2-diphenylethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2,2-bis(4-methoxyphenyl)ethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2,2-bis(4-methylphenyl)ethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2,2-bis(4-fluorophenyl)ethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2,2-bis(4-chlorophenyl)ethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-methoxyphenyl)ethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(2-methylphenyl)ethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-methylphenyl)ethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(2-fluorophenyl)ethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(2-chlorophenyl)ethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-chlorophenyl)ethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(3-bromophenyl)ethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-phenylphenyl)ethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-trifluoromethylphenyl)ethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-(3-chlorophenyl)-2-(4-chlorophenyl)ethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-styryltetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(3-chlorostyryl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(3-bromostyryl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-bromostyryl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenylprop-1-en-1-yl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate.

[0016] In the method for synthesizing 4-(2,2-diarylvinyl)thiobutyl phosphoric / phosphonic acid esters from 1-vinyl-tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate and organic phosphoric acid compounds, the organic phosphoric acid compounds are selected from one of diphenyl phosphoric acid, bis(3-methylphenyl)phosphoric acid, bis(4-methylphenyl)phosphoric acid, bis(4-methoxyphenyl)phosphoric acid, bis(3,5-dimethylphenyl)phosphoric acid, bis(1-naphthyl)phosphoric acid, bis(2-naphthyl)phosphoric acid, dicyclohexyl phosphoric acid, diphenoxy phosphoric acid, dibenzyloxy phosphoric acid, diethoxy phosphoric acid, dibutoxy phosphoric acid, bis(2-ethylhexoxy)phosphoric acid, di-tert-butoxy phosphoric acid, phenylethoxy phosphoric acid, phenylmethyl phosphoric acid, (2-ethylhexoxy)(2-ethylhexyl)phosphoric acid.

[0017] In the method for synthesizing 4-(2,2-diarylvinyl)thiobutyl phosphoric / phosphonic acid esters from 1-vinyl-tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate and organic phosphoric acid compounds, the molar ratio of 1-vinyl-tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate to organic phosphoric acid compounds is 1:[1.0 - 2.0]; the molar ratio of 1-vinyl-tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate to cuprous iodide is 1:[0.05 - 0.2]; the molar ratio of 1-vinyl-tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate to cesium carbonate is 1:[1.0 - 3.0].

[0018] Advantages of the present invention:

[0019] The method provided by the present invention for efficiently and highly selectively synthesizing 4-(2,2-diarylvinyl)thiobutyl phosphoric / phosphonic acid esters from 1-vinyl-tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate and organic phosphoric acid compounds has a mild and easily controllable reaction process. While achieving a high yield and 100% selectivity, this method is simple and easy to implement, and the catalysts used are inexpensive and easily available, with simple preparation and good industrial application prospects.

Specific Embodiments

[0020] The following further describes the present invention in conjunction with the embodiments of the present invention:

[0021] Testing and analysis:

[0022] In the following examples of the present invention, the structural analysis of the reaction products was carried out using a gas chromatography-mass spectrometry (GC / MS) instrument (6890N / 5973N) equipped with an HP-5MS capillary column (30 m × 0.45 mm × 0.8 μm) produced by Agilent and a Bruker Avance-III 500 nuclear magnetic resonance analyzer produced by Bruker. The selectivity and yield of the target product were analyzed using a Bruker Avance-III 500 nuclear magnetic resonance analyzer produced by Bruker.

[0023] Example 1

[0024] 80 mg (0.2 mmol) of 1-(2,2-diphenylethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 43.6 mg (0.2 mmol) of diphenylphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added into a Schlenk tube under an air atmosphere, and then 1.0 mL of ethyl acetate was added. The mixture was stirred and reacted at 80 °C for 3 hours. After the reaction was completed, the product was purified by column chromatography. The yield of the target product was 97%.

[0025] Example 2

[0026] 92 mg (0.2 mmol) of 1-(2,2-bis(4-methoxyphenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 43.6 mg (0.2 mmol) of diphenylphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added into a Schlenk tube under an air atmosphere, and then 1.0 mL of ethyl acetate was added. The mixture was stirred and reacted at 80 °C for 3 hours. After the reaction was completed, the product was purified by column chromatography. The yield of the target product was 96%.

[0027] Example 3

[0028] 85.6 mg (0.2 mmol) of 1-(2,2-bis(4-methylphenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 43.6 mg (0.2 mmol) of diphenylphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added into a Schlenk tube under an air atmosphere, and then 1.0 mL of ethyl acetate was added. The mixture was stirred and reacted at 80 °C for 3 hours. After the reaction was completed, the product was purified by column chromatography. The yield of the target product was 94%.

[0029] Example 4

[0030] 87.2 mg (0.2 mmol) of 1-(2,2-bis(4-fluorophenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 43.6 mg (0.2 mmol) of diphenylphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere, and then 1.0 mL of ethyl acetate was added. The mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography. The yield of the target product was 92%.

[0031] Example 5

[0032] 93.8 mg (0.2 mmol) of 1-(2,2-bis(4-chlorophenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 43.6 mg (0.2 mmol) of diphenylphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere, and then 1.0 mL of ethyl acetate was added. The mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography. The yield of the target product was 91%.

[0033] Example 6

[0034] 86 mg (0.2 mmol) of 1-(2-phenyl-2-(4-methoxyphenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 43.6 mg (0.2 mmol) of diphenylphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere, and then 1.0 mL of ethyl acetate was added. The mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography. The yield of the target product was 93%.

[0035] Example 7

[0036] 82.8 mg (0.2 mmol) of 1-(2-phenyl-2-(2-methylphenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 43.6 mg (0.2 mmol) of diphenylphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere, and then 1.0 mL of ethyl acetate was added. The mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography. The yield of the target product was 92%.

[0037] Example 8

[0038] 82.8 mg (0.2 mmol) of 1-(2-phenyl-2-(4-methylphenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 43.6 mg (0.2 mmol) of diphenylphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 95%.

[0039] Example 9

[0040] 86.8 mg (0.2 mmol) of 1-(2-phenyl-2-(2-chlorophenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 43.6 mg (0.2 mmol) of diphenylphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 88%.

[0041] Example 10

[0042] 95.8 mg (0.2 mmol) of 1-(2-phenyl-2-(3-bromophenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 43.6 mg (0.2 mmol) of diphenylphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 94%.

[0043] Example 11

[0044] 95.2 mg (0.2 mmol) of 1-(2-phenyl-2-(4-phenylphenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 43.6 mg (0.2 mmol) of diphenylphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 91%.

[0045] Example 12

[0046] 93.8 mg (0.2 mmol) of 1-(2-(3-chlorophenyl)-2-(4-chlorophenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 43.6 mg (0.2 mmol) of diphenylphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield was 89%.

[0047] Example 13

[0048] 64.8 mg (0.2 mmol) of 1-styryl tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 43.6 mg (0.2 mmol) of diphenylphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield was 96%.

[0049] Example 14

[0050] 80.6 mg (0.2 mmol) of 1-(3-bromostyryl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 43.6 mg (0.2 mmol) of diphenylphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield was 93%.

[0051] Example 15

[0052] 80.6 mg (0.2 mmol) of 1-(2-bromostyryl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 43.6 mg (0.2 mmol) of diphenylphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield was 86%.

[0053] Example 16

[0054] 80 mg (0.2 mmol) of 1-(2,2-diphenylethenyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 49.2 mg (0.2 mmol) of bis(3-methylphenyl)phosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 h. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 94%.

[0055] Example 17

[0056] 80 mg (0.2 mmol) of 1-(2,2-diphenylethenyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 49.2 mg (0.2 mmol) of bis(4-methylphenyl)phosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 h. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 95%.

[0057] Example 18

[0058] 80 mg (0.2 mmol) of 1-(2,2-diphenylethenyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 55.6 mg (0.2 mmol) of bis(4-methoxyphenyl)phosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 h. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 96%.

[0059] Example 19

[0060] 80 mg (0.2 mmol) of 1-(2,2-diphenylethenyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 54.8 mg (0.2 mmol) of bis(3,5-dimethylphenyl)phosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 h. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 95%.

[0061] Example 20

[0062] 80 mg (0.2 mmol) of 1-(2,2-diphenylethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 63.6 mg (0.2 mmol) of bis(1-naphthyl)phosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere, and then 1.0 mL of ethyl acetate was added. The mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 93%.

[0063] Example 21

[0064] 80 mg (0.2 mmol) of 1-(2,2-diphenylethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 63.6 mg (0.2 mmol) of bis(2-naphthyl)phosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere, and then 1.0 mL of ethyl acetate was added. The mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 94%.

[0065] Example 22

[0066] 80 mg (0.2 mmol) of 1-(2,2-diphenylethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 46 mg (0.2 mmol) of dicyclohexylphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere, and then 1.0 mL of ethyl acetate was added. The mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 94%.

[0067] Example 23

[0068] 80 mg (0.2 mmol) of 1-(2,2-diphenylethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 50 mg (0.2 mmol) of diphenoxyphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere, and then 1.0 mL of ethyl acetate was added. The mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 90%.

[0069] Example 24

[0070] 80 mg (0.2 mmol) of 1-(2,2-diphenylethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 55.6 mg (0.2 mmol) of dibenzyloxyphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 91%.

[0071] Example 25

[0072] 80 mg (0.2 mmol) of 1-(2,2-diphenylethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 30.8 mg (0.2 mmol) of diethoxyphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 91%.

[0073] Example 26

[0074] 80 mg (0.2 mmol) of 1-(2,2-diphenylethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 42 mg (0.2 mmol) of dibutoxyphosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 92%.

[0075] Example 27

[0076] 80 mg (0.2 mmol) of 1-(2,2-diphenylethynyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 64.4 mg (0.2 mmol) of bis(2-ethylhexyl)phosphoric acid, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 92%.

[0077] Example 28

[0078] 80 mg (0.2 mmol) of 1-(2,2-diphenylvinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 42 mg (0.2 mmol) of di-tert-butyl phosphite, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 81%.

[0079] Example 29

[0080] 80 mg (0.2 mmol) of 1-(2,2-diphenylvinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 37.2 mg (0.2 mmol) of phenylethyl phosphite, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 92%.

[0081] Example 30

[0082] 80 mg (0.2 mmol) of 1-(2,2-diphenylvinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 31.2 mg (0.2 mmol) of phenylmethyl phosphite, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 94%.

[0083] Example 31

[0084] 80 mg (0.2 mmol) of 1-(2,2-diphenylvinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 61.2 mg (0.2 mmol) of (2-ethylhexoxy)(2-ethylhexyl) phosphite, 3.8 mg (0.02 mmol) of copper(I) iodide, and 130.3 mg (0.4 mmol) of cesium carbonate were added to a Schlenk tube under an air atmosphere. Then, 1.0 mL of ethyl acetate was added, and the mixture was stirred at 80 °C for 3 hours. After the reaction was completed, the target product was purified by column chromatography, and the yield of the target product was 89%.

[0085] As can be seen from the above embodiments, the method for efficiently reacting 1-vinyl-tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate with organic phosphoric acid compounds to prepare corresponding 4-(2,2-diarylvinyl)thiobutyl phosphates / phosphonates containing different substituted functional groups adopted in the present invention has the advantages of mild reaction conditions, cheap and easily available catalysts, and simple preparation. In addition, this method also has the advantages of wide substrate applicability and high yield, providing a method for efficiently synthesizing 4-(2,2-diarylvinyl)thiobutyl phosphates / phosphonates derivatives containing different substituted functional groups.

[0086] The above-described embodiments merely represent several implementation manners of the present invention, and their descriptions are relatively specific and detailed, but should not be construed as limiting the scope of the patent of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the appended claims.

Claims

1. A method for preparing 4-(2,2-diarylvinyl)thiobutyl phosphorus / phosphonate, characterized in that: 1-vinyl-tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, an organic phosphoric acid compound, a catalyst, a base and an organic solvent are placed in a reaction container under air environment and mixed, and reacted at 25-120° C. for 3-6 hours under stirring to obtain 4-(2,2-diarylvinyl)thiobutylphosphine / phosphonate. The specific reaction formula is shown in formula (I): Wherein, the catalyst is cuprous iodide, the base is cesium carbonate, and the organic solvent is ethyl acetate; R 1 One selected from the group consisting of phenyl, 4-methoxyphenyl, 4-methylphenyl, 4-fluorophenyl, 4-chlorophenyl, a hydrogen atom, and a methyl group; R 2 One selected from phenyl, 4-methoxyphenyl, 4-methylphenyl, 4-fluorophenyl, 4-chlorophenyl, 2-methylphenyl, 2-fluorophenyl, 2-chlorophenyl, 3-bromophenyl, 4-phenylphenyl, 4-trifluoromethylphenyl, 3-chlorophenyl, and 2-bromophenyl; R 3 One selected from phenyl, 3-methylphenyl, 4-methylphenyl, 4-methoxyphenyl, 3,5-dimethylphenyl, 1-naphthyl, 2-naphthyl, cyclohexyl, phenoxy, benzyloxy, ethoxy, butoxy, 2-ethylhexyloxy, and tert-butoxy; R 4 One selected from phenyl, 3-methylphenyl, 4-methylphenyl, 4-methoxyphenyl, 3,5-dimethylphenyl, 1-naphthyl, 2-naphthyl, cyclohexyl, phenoxy, benzyloxy, ethoxy, butoxy, 2-ethylhexyl, 2-ethylhexyl, tert-butoxy, and methyl.

2. The method according to claim 1, characterized in that The 1-vinyl-tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate is selected from 1-(2,2-diphenylvinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2,2-bis(4-methoxyphenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2,2-bis(4-methylphenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2,2-bis(4-fluorophenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2,2-bis(4-chlorophenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, )tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-methoxyphenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(2-methylphenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-methylphenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(2-fluorophenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(2 -chlorophenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-chlorophenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(3-bromophenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-phenylphenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-trifluoromethylphenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, -(3-chlorophenyl)-2-(4-chlorophenyl)vinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-phenylvinyltetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(3-chlorophenylvinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(3-bromostyryl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-bromostyryl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenylprop-1-en-1-yl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate.

3. The method according to claim 1, characterized in that The organic phosphoric acid compound is selected from one of diphenyl phosphoric acid, di(3-methylphenyl)phosphoric acid, di(4-methylphenyl)phosphoric acid, di(4-methoxyphenyl)phosphoric acid, di(3,5-dimethylphenyl)phosphoric acid, di(1-naphthyl)phosphoric acid, di(2-naphthyl)phosphoric acid, dicyclohexyl phosphoric acid, diphenoxy phosphoric acid, dibenzyloxy phosphoric acid, diethoxy phosphoric acid, dibutoxy phosphoric acid, di(2-ethylhexyloxy)phosphoric acid, di-tert-butoxy phosphoric acid, phenylethoxy phosphoric acid, phenylmethyl phosphoric acid, and (2-ethylhexyloxy) (2-ethylhexyl) phosphoric acid.

4. The method according to claim 1, characterized in that The molar ratio of the 1-vinyl-tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate to the organic phosphoric acid compound is 1:[1.0-2.0]; the molar ratio of the 1-vinyl-tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate to cuprous iodide is 1:[0.05-0.2]; the molar ratio of the 1-vinyl-tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate to cesium carbonate is 1:[1.0-3.0].

Images