Method for preparing S-(4-(2, 2-diaryl vinyl) thiobutyl) selenium / tellurium phosphorus / phosphonate

Abstract

The invention provides a method for efficiently and highly selectively synthesizing S-(4-(2, 2-diaryl vinyl) thiobutyl) selenium / tellurium phosphorus / phosphonate compounds containing different substituted functional groups, which adopts copper trifluoromethanesulfonate as a catalyst to synthesize the S-(4-(2, 2-diaryl vinyl) thiobutyl) selenium / tellurium phosphorus / phosphonate compounds containing different substituted functional groups. According to the method, 1-vinyl-tetrahydro-1H-thiophene-1-onium trifluoromethanesulfonate, a P (III)-nucleophilic reagent (trialkyl phosphite and alkoxy dialkyl phosphine) and selenium powder or tellurium powder are used as reaction substrates, and an organic solvent, alkali and an auxiliary agent 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. The method overcomes the defects of poor reaction selectivity, tedious reaction steps, low yield, need of a noble metal catalyst and reagents harmful to the environment and the like in the traditional synthesis of S-(4-(2, 2-diaryl vinyl) thiobutyl) selenium / tellurium phosphorus / phosphonate compounds, and has a good industrial application prospect. The invention also provides corresponding S-(4-(2, 2-diaryl vinyl) thiobutyl) selenium / tellurium phosphorus / phosphonate derivatives containing different substituted functional groups at the same time.

Description

Technical Field

[0001] The present invention relates to S The present invention relates to the field of catalytic synthesis of -(4-(2,2-diarylvinyl)thiobutyl)selenium / tellurylphosphorus / phosphonate compounds, specifically to a 1-vinyl-tetrahydro-1- H -Thiophen-1-ium triflate is efficiently prepared by reacting with P(III)-nucleophiles (trialkyl phosphites, alkoxydialkyl phosphines) and selenium powder or tellurium powder S -(4-(2,2-diarylvinyl)thiobutyl)selenium / tellurium phosphorus / phosphonate derivatives. Background Art

[0002] Selenium / tellurium substituted phosphorus / phosphonate compounds are an important class of organic synthesis intermediates. Due to the special properties of heteroatoms such as phosphorus, selenium, and tellurium in their molecules, they are widely used in pesticides, insecticides, pharmaceutical intermediates, biological agents, flame retardant materials, optoelectronic materials, and organic synthesis.

[0003] The methods for synthesizing selenium / tellurium phosphine / phosphonate compounds reported in the literature mainly include: (1) Cross-coupling reaction: using PH compounds and diselenide or ditelluride compounds to undergo cross-coupling reaction under the promotion of transition metals, organic ligands (carbene, phosphine and amine, etc.) and bases. However, the above reaction has defects such as poor selectivity and poor water-oxygen stability. In addition, the reaction reagents have a foul odor, poor functional group tolerance, high reaction cost, and toxic reaction waste liquid, which requires special treatment; (2) Online activation reaction of selenium powder or tellurium powder: online activation of PH bond-containing compounds with selenium powder to form P-Se compounds, which then undergo cross-coupling reaction with halogenated alkanes or diazo compounds; for tellurium powder, it is usually necessary to use special phosphine ligands such as PR3 to form R3P=Te compounds online activation, and then prepare the corresponding organic tellurium compounds. So far, there are few literatures on the direct activation of tellurium powder. However, the above methods generally use environmentally unfriendly reagents (diazonium salts, thiols, thiophenols, etc.) and special ligands (phosphine-based, carbene-based ligands, etc.). The activation process of tellurium powder also requires an equivalent amount of phosphine reagent as a sacrificial agent. In addition, the above processes also have defects such as cumbersome experimental steps, expensive and difficult to recycle catalysts, harsh reaction conditions, cross-substrate applicability, low selectivity and yield, and greater environmental pollution.

[0004] So far, SThe efficient synthesis of -(4-(2,2-diarylvinyl)thiobutyl)selenium / tellurium phosphine / phosphonate compounds faces several problems, such as raw material quality, production safety (toxicity of diselenide and ditelluride compounds), and product stability and purity. The synthesis technology is difficult, and currently only a few companies in the United States and Germany are producing them. However, most of the special functionalized compounds in my country are S At present, products such as -(4-(2,2-diarylvinyl)thiobutyl)selenium / tellurium phosphorus / phosphonate compounds mainly rely on imports.

[0005] In view of the shortcomings of the existing synthesis process, the industry is focusing on the use of cheap catalysts to efficiently catalyze the development of the corresponding synthesis of stable, cheap and readily available raw materials. S -(4-(2,2-Diarylvethenyl)thiobutyl)selenium / tellurium phosphorus / phosphonate compounds. Summary of the invention

[0006] The object of the present invention is to provide a kind of 1-vinyl-tetrahydro-1- H -Thiophen-1-ium triflate and P(III)-nucleophile (trialkyl phosphite, alkoxydialkylphosphine) and selenium powder or tellurium powder as raw materials to efficiently and selectively synthesize the corresponding S -(4-(2,2-diarylvinyl)thiobutyl)selenium / tellurylphosphorus / phosphonate compounds to overcome the above-mentioned defects in the prior art.

[0007] The present invention comprises the following steps: taking a reaction amount of 1-vinyl-tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, P(III)-nucleophile (trialkyl phosphite, alkoxydialkylphosphine), selenium powder or tellurium powder, catalyst, base, auxiliary agent and organic solvent are placed in a reaction vessel under nitrogen atmosphere and mixed, and stirred at 25-120 o C for 3 to 6 hours to obtain the corresponding compounds containing different substituted functional groups. S -(4-(2,2-diarylvinyl)thiobutyl)selenium / tellurium phosphorus / phosphonate compounds. The specific reaction formula is as follows: （I） in, The catalyst is copper trifluoromethanesulfonate, the base is potassium carbonate, the auxiliary agent is water, and the organic solvent is ethyl acetate; R 1 is selected from the group consisting of phenyl, 4-methoxyphenyl, 4-methylphenyl, 4-fluorophenyl, 4-chlorophenyl, a hydrogen atom, and a methyl group; R 2Selected from 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; R 3 Selected from methoxy, ethoxy, isopropoxy, butoxy, 2-ethyl-hexyloxy, cyclohexyl; R 4 Selected from methoxy, ethoxy, isopropoxy, butoxy, 2-ethyl-hexyloxy, cyclohexyl; R 5 Selected from methoxy, ethoxy, isopropoxy, butoxy, 2-ethyl-hexyloxy.

[0008] The above-mentioned 1-vinyl-tetrahydro-1 H -Synthesis of 1-thiophene-1-ium triflate with P(III)-nucleophile (trialkyl phosphite, alkoxydialkylphosphine) and selenium powder or tellurium powder S -(4-(2,2-diarylvinyl)thiobutyl)selenium / tellurylphosphorus / phosphonate compounds, 1-vinyl-tetrahydro-1 H -Thiophen-1-ium triflate selected from 1-(2,2-diphenylvinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2,2-bis(4-methoxyphenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2,2-di(4-methylphenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2,2-bis(4-fluorophenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2,2-bis(4-chlorophenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-methoxyphenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(2-methylphenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-methylphenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(2-fluorophenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(2-chlorophenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-chlorophenyl)vinyl)tetrahydro-1 H-Thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(3-bromophenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-phenylphenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-trifluoromethylphenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2-(3-chlorophenyl)-2-(4-chlorophenyl)vinyl)tetrahydro-1 H -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.

[0009] The above-mentioned 1-vinyl-tetrahydro-1 H -Synthesis of 1-thiophene-1-ium triflate with P(III)-nucleophile (trialkyl phosphite, alkoxydialkylphosphine) and selenium powder or tellurium powder S -(4-(2,2-diarylvinyl)thiobutyl)selenium / tellurylphosphine / phosphonate compound method, P(III)-nucleophile (trialkylphosphite, alkoxydialkylphosphine) is selected from triethylphosphite, trimethylphosphite, tributylphosphite, triisopropylphosphite, tri(2-ethyl-hexyloxy)phosphite, ethoxydicyclohexylphosphine, ethoxydiphenylphosphine, ethoxydi(2-methylphenyl)phosphine, ethoxydi(3-methylphenyl)phosphine )phosphine, ethoxybis(4-methylphenyl)phosphine, ethoxybis(4-methoxyphenyl)phosphine, ethoxybis(4-ethylphenyl)phosphine, ethoxybis(4-fluorophenyl)phosphine, ethoxybis(3-chlorophenyl)phosphine, ethoxybis(4-chlorophenyl)phosphine, ethoxybis(3,5-dimethylphenyl)phosphine, ethoxybis(4-phenylphenyl)phosphine, ethoxybis(1-naphthyl)phosphine, ethoxybis(2-naphthyl)phosphine, (3-fluorophenyl)(ethoxy)phenylphosphine.

[0010] The above-mentioned 1-vinyl-tetrahydro-1 H -Synthesis of 1-thiophene-1-ium triflate with P(III)-nucleophile (trialkyl phosphite, alkoxydialkylphosphine) and selenium powder or tellurium powder S -(4-(2,2-diarylvinyl)thiobutyl)selenium / tellurylphosphorus / phosphonate compounds, the 1-vinyl-tetrahydro-1 HThe molar ratio of 1-thiophene-1-ium trifluoromethanesulfonate to selenium powder or tellurium powder and P(III)-nucleophile is 1:[0.2~0.5]:[1.0~2.0]; 1-vinyl-tetrahydro-1 H The molar ratio of 1-thiophene-1-ium trifluoromethanesulfonate to copper trifluoromethanesulfonate is 1:[0.05~0.2]; 1-vinyl-tetrahydro-1 H The molar ratio of 1-thiophene-1-ium trifluoromethanesulfonate to potassium carbonate is 1:[1.0~3.0]; 1-vinyl-tetrahydro-1 H The molar ratio of thiophen-1-ium trifluoromethanesulfonate to water is 1:[1.0~3.0].

[0011] The present invention provides 1-vinyl-tetrahydro-1 H -Efficient and highly selective synthesis of thiophen-1-ium trifluoromethanesulfonate with P(III)-nucleophiles (trialkyl phosphites, alkoxydialkylphosphines) and selenium or tellurium powder S -(4-(2,2-diarylvinyl)thiobutyl)selenium / tellurylphosphorus / phosphonate compounds, the reaction process is mild and easy to control. While obtaining a high yield and 100% selectivity, the method is simple and easy to operate, and the catalyst used is cheap and easy to obtain, the preparation is simple, and has good industrial application prospects. DETAILED DESCRIPTION

[0012] The present invention will be further described below in conjunction with embodiments of the present invention: 1. Testing and Analysis The structural analysis of the reaction products in the following examples of the present invention was performed using a gas phase-mass spectrometer GC / MS (6890N / 5973N) equipped with an HP-5MS capillary chromatographic column (30m×0.45mm×0.8μm) 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. 2. Embodiment Example 1

[0013] 80 mg (0.2 mmol) of 1-(2,2-diphenylethenyl)tetrahydro-1- H1-thiophen-1-ium trifluoromethanesulfonate, 33.2 mg (0.2 mmol) of triethyl phosphite, 15.8 mg (0.04 mmol) of selenium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 83%. Example 2

[0014] 80 mg (0.2 mmol) of 1-(2,2-diphenylethenyl)tetrahydro-1- H 1-thiophen-1-ium trifluoromethanesulfonate, 50 mg (0.2 mmol) of tributyl phosphite, 15.8 mg (0.04 mmol) of selenium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 80%. Example 3

[0015] 80 mg (0.2 mmol) of 1-(2,2-diphenylethenyl)tetrahydro-1- H 1-thiophen-1-ium trifluoromethanesulfonate, 41.6 mg (0.2 mmol) of triisopropyl phosphite, 15.8 mg (0.04 mmol) of selenium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. The mixture was heated at 80 °C. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 82%. Example 4

[0016] 80 mg (0.2 mmol) of 1-(2,2-diphenylethenyl)tetrahydro-1- H1-thiophen-1-ium trifluoromethanesulfonate, 48.4 mg (0.2 mmol) of ethoxydicyclohexylphosphine, 15.8 mg (0.04 mmol) of selenium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. The mixture was heated at 80 °C. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 81%. Example 5

[0017] 80.6 mg (0.2 mmol) of 1-(2-bromostyryl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 33.2 mg (0.2 mmol) of triethyl phosphite, 15.8 mg (0.04 mmol) of selenium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 86%. Example 6

[0018] 80.6 mg (0.2 mmol) of 1-(3-bromostyryl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 33.2 mg (0.2 mmol) of triethyl phosphite, 15.8 mg (0.04 mmol) of selenium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 87%. Example 7

[0019] 83.6 mg (0.2 mmol) of 1-(2-phenyl-2-(4-fluorophenyl)vinyl)tetrahydro-1- H1-thiophen-1-ium trifluoromethanesulfonate, 33.2 mg (0.2 mmol) of triethyl phosphite, 15.8 mg (0.04 mmol) of selenium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 86%. Example 8

[0020] 95.8 mg (0.2 mmol) of 1-(2-phenyl-2-(4-bromophenyl)vinyl)tetrahydro-1- H 1-thiophen-1-ium trifluoromethanesulfonate, 33.2 mg (0.2 mmol) of triethyl phosphite, 15.8 mg (0.04 mmol) of selenium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 85%. Example 9

[0021] 93.8 mg (0.2 mmol) of 1-(2,2-bis(4-chlorophenyl)vinyl)tetrahydro-1- H 1-thiophen-1-ium trifluoromethanesulfonate, 33.2 mg (0.2 mmol) of triethyl phosphite, 15.8 mg (0.04 mmol) of selenium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 89%. Example 10

[0022] 86 mg (0.2 mmol) of 1-(2-phenyl-2-(4-methoxyphenyl)vinyl)tetrahydro-1- H1-thiophen-1-ium trifluoromethanesulfonate, 33.2 mg (0.2 mmol) of triethyl phosphite, 15.8 mg (0.04 mmol) of selenium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. The mixture was heated at 80 °C. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 83%. Embodiment 11

[0023] 82.8 mg (0.2 mmol) of 1-(2-phenyl-2-(3-methylphenyl)ethenyl)tetrahydro-1- H 1-thiophen-1-ium trifluoromethanesulfonate, 33.2 mg (0.2 mmol) of triethyl phosphite, 15.8 mg (0.04 mmol) of selenium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. The mixture was heated at 80 °C. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 80%. Example 12

[0024] 82.8 mg (0.2 mmol) of 1-(2-phenyl-2-(4-methylphenyl)ethenyl)tetrahydro-1- H 1-thiophen-1-ium trifluoromethanesulfonate, 33.2 mg (0.2 mmol) of triethyl phosphite, 15.8 mg (0.04 mmol) of selenium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. The mixture was heated at 80 °C. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 82%. Example 13

[0025] 80 mg (0.2 mmol) of 1-(2,2-diphenylethenyl)tetrahydro-1- H1-thiophen-1-ium trifluoromethanesulfonate, 33.2 mg (0.2 mmol) of triethyl phosphite, 25.5 mg (0.04 mmol) of tellurium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. The mixture was heated at 80 °C. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 81%. Embodiment 14

[0026] 80 mg (0.2 mmol) of 1-(2,2-diphenylethenyl)tetrahydro-1- H 2-thiophen-1-ium trifluoromethanesulfonate, 24.8 mg (0.2 mmol) of trimethyl phosphite, 25.5 mg (0.04 mmol) of tellurium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. The mixture was heated at 80 °C. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 88%. Embodiment 15

[0027] 80 mg (0.2 mmol) of 1-(2,2-diphenylethenyl)tetrahydro-1- H 1-thiophen-1-ium trifluoromethanesulfonate, 50 mg (0.2 mmol) of tributyl phosphite, 25.5 mg (0.04 mmol) of tellurium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. The mixture was heated at 80 °C. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 82%. Example 16

[0028] 80 mg (0.2 mmol) of 1-(2,2-diphenylethenyl)tetrahydro-1- H1-thiophen-1-ium trifluoromethanesulfonate, 41.6 mg (0.2 mmol) of triisopropyl phosphite, 25.5 mg (0.04 mmol) of tellurium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. The mixture was heated at 80 °C. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 77%. Embodiment 17

[0029] 80 mg (0.2 mmol) of 1-(2,2-diphenylethenyl)tetrahydro-1- H 1-thiophen-1-ium trifluoromethanesulfonate, 93.6 mg (0.2 mmol) of tris(2-ethyl-hexyloxy)phosphite, 25.5 mg (0.04 mmol) of tellurium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. The mixture was stirred at 80 °C for 2 h. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 68%. Embodiment 18

[0030] 80 mg (0.2 mmol) of 1-(2,2-diphenylethenyl)tetrahydro-1- H 1-thiophen-1-ium trifluoromethanesulfonate, 48.4 mg (0.2 mmol) of ethoxydicyclohexylphosphine, 25.5 mg (0.04 mmol) of tellurium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. The mixture was heated at 80 °C. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 79%. Embodiment 19

[0031] 87.2 mg (0.2 mmol) of 1-(2,2-bis(4-fluorophenyl)vinyl)tetrahydro-1- H1-thiophen-1-ium trifluoromethanesulfonate, 33.2 mg (0.2 mmol) of triethyl phosphite, 25.5 mg (0.04 mmol) of tellurium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 79%. Embodiment 20

[0032] 93.8 mg (0.2 mmol) of 1-(2,2-bis(4-chlorophenyl)vinyl)tetrahydro-1- H 1-thiophen-1-ium trifluoromethanesulfonate, 33.2 mg (0.2 mmol) of triethyl phosphite, 25.5 mg (0.04 mmol) of tellurium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 76%. Embodiment 21

[0033] 92 mg (0.2 mmol) of 1-(2,2-bis(4-methoxyphenyl)vinyl)tetrahydro-1- H 1-thiophen-1-ium trifluoromethanesulfonate, 33.2 mg (0.2 mmol) of triethyl phosphite, 25.5 mg (0.04 mmol) of tellurium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 72%. Embodiment 22

[0034] 86 mg (0.2 mmol) of 1-(2-phenyl-2-(4-methoxyphenyl)vinyl)tetrahydro-1- H1-thiophen-1-ium trifluoromethanesulfonate, 33.2 mg (0.2 mmol) of triethyl phosphite, 25.5 mg (0.04 mmol) of tellurium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. The mixture was stirred at 80 °C for 2 h. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 74%. Embodiment 23

[0035] 93.8 mg (0.2 mmol) of 1-(2-(3-chlorophenyl)-2-(4-chlorophenyl)vinyl)tetrahydro-1- H 1-thiophen-1-ium trifluoromethanesulfonate, 33.2 mg (0.2 mmol) of triethyl phosphite, 25.5 mg (0.04 mmol) of tellurium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 77%. Embodiment 24

[0036] 86 mg (0.2 mmol) of 1-(2-phenyl-2-(4-methoxyphenyl)vinyl)tetrahydro-1- H 1-thiophen-1-ium trifluoromethanesulfonate, 33.2 mg (0.2 mmol) of triethyl phosphite, 25.5 mg (0.04 mmol) of tellurium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. The mixture was stirred at 80 °C for 2 h. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 73%. Embodiment 25

[0037] 65.2 mg (0.2 mmol) of 1-(4-fluorophenylvinyl)tetrahydro-1H-thiophen-1-ium trifluoromethanesulfonate, 33.2 mg (0.2 mmol) of triethyl phosphite, 25.5 mg (0.04 mmol) of tellurium powder, 14.5 mg (0.04 mmol) of copper trifluoromethanesulfonate, 27.6 mg (0.2 mmol) of potassium carbonate and 7.2 mg (0.4 mmol) of water were placed in a Schlenk tube under air atmosphere, and 1.0 mL of ethyl acetate was added. The mixture was stirred at 80 °C for 2 h. o C and stirred for 3 hours. After the reaction was completed, the product was separated and purified by column chromatography, and the yield of the target product was 78%.

[0038] It can be seen from the above examples that the present invention uses 1-vinyl-tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate reacts efficiently with P(III)-nucleophiles (trialkyl phosphites, alkoxydialkyl phosphines) and sulfur powder to prepare the corresponding S -(4-(2,2-diarylvinyl)thiobutyl)selenium / tellurylphosphorus / phosphonate compounds have the advantages of mild reaction conditions, cheap and readily available catalysts, and simple preparation. In addition, this method also has the advantages of wide substrate applicability and high yield, providing a high-efficiency synthesis of substituted functional groups containing different S -(4-(2,2-diarylvinyl)thiobutyl)selenium / tellurium phosphorus / phosphonate derivatives.

[0039] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it 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, which 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 attached claims.

Claims

1. A 1-vinyl-tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate reacts with a P(III)-nucleophile (trialkyl phosphite, alkoxydialkylphosphine) and selenium powder or tellurium powder to prepare a compound having the structural formula （I） middle S -(4-(2,2-diarylvinyl)thiobutyl)selenium / tellurium phosphorus / phosphonate compound preparation method, the specific reaction formula is as follows: （I） It is characterized in that The following steps are included: Take the reaction amount of 1-vinyl-tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, P(III)-nucleophile (trialkyl phosphite, alkoxydialkylphosphine), selenium powder or tellurium powder, catalyst, base, auxiliary agent and organic solvent are placed in a reaction vessel under nitrogen atmosphere and mixed, and stirred at 25-120 o C for 3 to 6 hours to obtain the corresponding compounds containing different substituted functional groups. S -(4-(2,2-diarylvinyl)thio)butyl)selenium / tellurium phosphorus / phosphonate compounds; in, The catalyst is copper trifluoromethanesulfonate, the base is potassium carbonate, the auxiliary agent is water, and the organic solvent is ethyl acetate; R 1 is selected from the group consisting of phenyl, 4-methoxyphenyl, 4-methylphenyl, 4-fluorophenyl, 4-chlorophenyl, a hydrogen atom, and a methyl group; R 2 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, 2-bromophenyl; R 3 Selected from methoxy, ethoxy, isopropoxy, butoxy, 2-ethyl-hexyloxy, cyclohexyl; R 4 Selected from methoxy, ethoxy, isopropoxy, butoxy, 2-ethyl-hexyloxy, cyclohexyl; R 5 Selected from methoxy, ethoxy, isopropoxy, butoxy, 2-ethyl-hexyloxy.

2. The preparation method according to claim 1, characterized in that: The 1-vinyl-tetrahydro-1 H -Thiophen-1-ium triflate selected from 1-(2,2-diphenylvinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2,2-bis(4-methoxyphenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2,2-di(4-methylphenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2,2-bis(4-fluorophenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2,2-bis(4-chlorophenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-methoxyphenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(2-methylphenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-methylphenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(2-fluorophenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(2-chlorophenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-chlorophenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(3-bromophenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-phenylphenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2-phenyl-2-(4-trifluoromethylphenyl)vinyl)tetrahydro-1 H -Thiophen-1-ium trifluoromethanesulfonate, 1-(2-(3-chlorophenyl)-2-(4-chlorophenyl)vinyl)tetrahydro-1 H -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.

3. The preparation method according to claim 1, characterized in that: The P(III)-nucleophile (trialkyl phosphite, alkoxydialkyl phosphine) is selected from triethyl phosphite, trimethyl phosphite, tributyl phosphite, triisopropyl phosphite, tri(2-ethyl-hexyloxy) phosphite, and ethoxydicyclohexylphosphine.

4. The preparation method according to claim 1, characterized in that: The 1-vinyl-tetrahydro-1 H The molar ratio of 1-thiophene-1-ium trifluoromethanesulfonate to selenium powder or tellurium powder and P(III)-nucleophile is 1:[0.2~0.5]:[1.0~2.0]; 1-vinyl-tetrahydro-1 H The molar ratio of 1-thiophene-1-ium trifluoromethanesulfonate to copper trifluoromethanesulfonate is 1:[0.05~0.2]; 1-vinyl-tetrahydro-1 H The molar ratio of 1-thiophene-1-ium trifluoromethanesulfonate to potassium carbonate is 1:[1.0~3.0]; 1-vinyl-tetrahydro-1 H The molar ratio of thiophen-1-ium trifluoromethanesulfonate to water is 1:[1.0~3.0].

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