A method for catalytic synthesis of (E)-beta-thio vinyl sulfone compounds by using organic semiconductor carbon nitride

Abstract

The application provides a method for catalytically synthesizing (E)-beta-thio vinyl sulfone compounds by using organic semiconductor carbon nitride, and relates to the technical field of organic synthesis. The synthesis method provided by the application uses thiosulfonate and alkyne compounds as reaction substrates, uses graphite phase carbon nitride g-C3N4 prepared by urea thermal polycondensation as a heterogeneous photocatalyst, and makes the atom transfer radical addition reaction occur under the condition of an organic solvent and light to obtain the (E)-beta-thio vinyl sulfone compound. The application provides a new path for the synthesis of (E)-beta-thio vinyl sulfone compounds, and the yield is high. The synthesis method of the application uses organic semiconductor carbon nitride as a photocatalyst, and has the advantages of easy availability of raw materials, simple process, mild reaction conditions, green environmental protection and the like. The synthesis method of the application has wide substrate applicability, and can be used to synthesize various (E)-beta-thio vinyl sulfone compounds by using different substrates.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis, in particular to a method for catalytic synthesis of (E)-β-thio vinyl sulfone compounds by using organic semiconductor carbon nitride. BACKGROUND

[0002] Alkenyl sulfone compounds exist widely in many natural products and bioactive molecules, such as cysteine protease inhibitors, anti-trypanosomiasis agents, papain inhibitors, etc. In addition, alkenyl sulfone compounds have unique molecular structures (containing unsaturated carbon-carbon double bonds and sulfone groups, making them very important synthetic building blocks in organic transformations. A series of β-functionalized alkenyl sulfone compounds are synthesized by using metal complexes of Ir, Cu, Co, etc. as photocatalysts, however, the stereoselectivity of the alkenyl sulfone compounds generated by the reaction is poor, the transition metal catalyst is not easy to separate from the reaction mixture, especially in the late functionalization and drug preparation, metal residues are easy to exist, and the use of noble metals leads to difficulty in large-scale preparation of the reaction. Therefore, it is necessary to develop a new method for catalytic synthesis of alkenyl sulfone compounds.

[0003] Organic semiconductor carbon nitride (g-C3N4) can absorb light energy in the visible light range and generate charge separation and transmission, so that g-C3N4 has potential for wide application in the fields of photocatalysis, photoelectrochemistry and optoelectronic devices. However, there is no related report in the prior art about using semiconductor carbon nitride as a catalyst for synthesizing (E)-β-thio vinyl sulfone compounds. SUMMARY

[0004] The main purpose of the present application is to provide a method for catalytic synthesis of (E)-β-thio vinyl sulfone compounds under the action of light by using organic semiconductor carbon nitride (g-C3N4).

[0005] To achieve the above-mentioned purpose, the present application provides a method for catalytic synthesis of (E)-β-thio vinyl sulfone compounds by using organic semiconductor carbon nitride, which comprises the following steps: using thiosulfonate and alkyne compound as reaction substrates, using graphite phase carbon nitride g-C3N4 as a heterogeneous photocatalyst, and carrying out atom transfer radical addition reaction under the conditions of organic solvent and light irradiation, and then filtering, recrystallizing or chromatographing to purify to obtain the (E)-β-thio vinyl sulfone compound.

[0006] The reaction equation is as follows:

[0007]

[0008] Among them, the compound of formula (I) is an alkyne compound, R 1 selected from aryl, heteroaryl, alkyl, alkenyl;

[0009] The compound of formula (II) is a thiosulfonate, R 2 is aryl.

[0010] The present application has the following advantages using g-C3N4 as catalyst: (1) g-C3N4 is easy to prepare and has excellent chemical and thermal stability (600℃ without decomposition), more importantly, g-C3N4 is easy to separate from the reaction system and can be recycled multiple times; (2) the maximum absorption wavelength of g-C3N4 is 460 nm in the visible light region, and the reaction catalyzed by g-C3N4 does not need to use ultraviolet light, and the band gap of g-C3N4 under light can reach 2.7 eV; (3) the organic conversion catalyzed by g-C3N4 does not need to use transition metals, and there is no problem of metal residues in the late functionalization and synthesis of drugs; (4) g-C3N4 can be well compatible with organic phosphorus and organic sulfur and other reaction reagents that can easily poison transition metal catalysts and make them lose activity; (5) g-C3N4 has convenient controllability: by doping, introducing defects and adjusting the two-dimensional morphology of g-C3N4, g-C3N4 can be applied to different reaction types. Therefore, compared with traditional homogeneous photocatalysts such as Ru(II), Ir(III) and other noble metal complexes and organic dyes such as eosin Y, rose red and inorganic semiconductors such as CdS, the use of convenient and adjustable and recyclable organic semiconductor g-C3N4 as a heterogeneous photocatalyst realizes the atom transfer radical addition (ATRA) of alkyne under metal-free conditions.

[0011] Further, the thiosulfonate includes aryl thiosulfonate substituted by one or more substituents, wherein the substituents are selected from methyl, methoxy, benzyloxy, halogen group.

[0012] Further, the alkyne compound includes aryl alkyne compound, heteroaryl alkyne compound, C1-C6 alkyl alkyne compound, C3-C6 cycloalkyl alkyne compound or alkenyl alkyne compound substituted by one or more substituents. 16 The alkyne compound includes at least one of straight-chain or branched-chain alkyl alkyne compound, C3-C6 cycloalkyl alkyne compound or alkenyl alkyne.

[0013] Further, the substituents in the aryl alkyne compound substituted by one or more substituents are selected from methoxy, halogen group, trifluoromethyl, aldehyde group, methyl formate group, ketone group, methyl, ethyl; the heteroaryl group in the heteroaryl alkyne compound is selected from naphthyl, pyridyl, pyrrolyl, quinolyl, thienyl.

[0014] Further, the organic solvent includes at least one of dimethyl sulfoxide, ethylene glycol dimethyl ether, acetonitrile, ethyl acetate, dichloromethane.

[0015] Further, the light irradiation condition is stirring under blue LED light, and the stirring time is 17-72 h.

[0016] Further, the molar ratio of the acetylene compound to the thiosulfonate is 1:(2-5).

[0017] Further, the molar ratio of the acetylene compound to the g-C3N4 is 1:(0.4-2.0).

[0018] When the ratio is not within the range, the yield is low or no product is generated. For example, when the molar ratio of the acetylene compound, such as aryl acetylene compound, to the thiosulfonate is 1:(3-6), it can be observed that the yield of the generated product is very low, and E and Z forms exist simultaneously at a molar ratio of 1:6, lacking stereoselectivity. Too large a ratio is useless or even reduces the yield, and too small a ratio does not generate a product or the yield is extremely low.

[0019] Further, the molar ratio of the acetylene compound to the thiosulfonate is 1:(2-5).

[0020] When the acetylene compound is a heteroaryl acetylene compound, the molar ratio of the acetylene compound to the thiosulfonate is 1:5, the yield is higher than that of the molar ratio of 1:2.

[0021] Further, the molar ratio of the acetylene compound to the thiosulfonate is 1:(2-5).

[0022] Further, the molar ratio of the acetylene compound to the thiosulfonate is 1:(2-5).

[0023] When the molar ratio of the acetylene compound, such as aryl acetylene compound, to the thiosulfonate is 1:(3-7), it can be observed that the yield of the generated product is very low, and E and Z forms exist simultaneously at a molar ratio of 1:(6-7), lacking stereoselectivity.

[0024] Further, the preparation method of the g-C3N4 is: (1) adding urea into a crucible with a cover, heating and reacting for 3.5-4.5 h to 540-560℃ to obtain a yellow solid, and cooling to room temperature; (2) further heating and reacting the yellow solid in an open crucible for 1.5-2.5 h to 490-510℃ to obtain g-C3N4.

[0025] Further, the preparation method of the g-C3N4 is: (1) adding urea in a crucible with a cover, heating reaction for 4h to 550 DEG C, obtaining a yellow solid, cooling to room temperature; (2) further heating reaction of the yellow solid in an open crucible for 2h to 500 DEG C, obtaining g-C3N4.

[0026] Further, the heating reaction rate in the step (1) is 2.5 DEG C / min, and the further heating reaction rate in the step (2) is 5 DEG C / min.

[0027] Through a large number of experiments, it is found that the g-C3N4 prepared in the application can provide more photocatalytic reaction sites in the reaction system of the application, has high photocatalytic activity and high photocatalytic stability, and the catalytic effect is better than that of the commercially available g-C3N4, and the preparation method of the application is simple, good in repeatability, easy to operate and low in preparation cost.

[0028] In the application, when the alkyne compound is an aryl alkyne compound (such as phenylacetylene), the chemical equation for synthesizing the alkyl aryl alkyne compound is as shown in the following formula (IV),

[0029]

[0030] Among them, the organic solvent is at least one of dimethyl sulfoxide, ethylene glycol dimethyl ether, acetonitrile, ethyl acetate and dichloromethane.

[0031] In the alkyne compound, according to the difference of R 1 group, the alkyne compound can include the following types:

[0032] a) aryl alkyne compound

[0033]

[0034] b) heteroaryl alkyne compound

[0035]

[0036] c) alkyl alkyne compound

[0037]

[0038] d) alkyne generated by anti-inflammatory drugs and bioactive molecules

[0039]

[0040] In the thiosulfonate, according to the difference of the substituent group R 2 , the thiosulfonate is:

[0041]

[0042] Accordingly, the substituent group in the structure of the synthesized (E)-beta-thio vinyl sulfone compound changes accordingly.

[0043] Compared with the prior art, the present application has the following advantages:

[0044] (1) The technical scheme of the present application provides a new path for the synthesis of (E)-beta-thio vinyl sulfone compounds. The yield of (E)-beta-thio vinyl sulfone compounds prepared by the above-mentioned synthetic route of the present application is higher.

[0045] (2) The present application uses organic semiconductor carbon nitride (g-C3N4) as a photocatalyst, which is beneficial to environmental protection and reduces the use of transition metal ion catalysts.

[0046] (3) The synthesis method of the present application uses organic semiconductor carbon nitride (g-C3N4) as a photocatalyst, which has the advantages of easy availability of raw materials, simple process, mild reaction conditions, green environmental protection, etc.

[0047] (4) The synthesis method of the present application has wide substrate applicability, and can be used to synthesize various (E)-beta-thio vinyl sulfone compounds with different substrates.

[0048] (5) The product of the present application can be used as a synthetic intermediate and design various bioactive molecules as an important structural unit in drug molecules, which has a broad application prospect in the fields of medical anti-inflammatory, antibacterial, antiviral, antitumor, etc.

[0049] (6) The g-C3N4 prepared in the present application can provide more photocatalytic reaction sites in the reaction system of the present application, has high photocatalytic activity and high photocatalytic stability, and the preparation method is simple, reproducible and easy to operate, which is beneficial to reduce the cost. DETAILED DESCRIPTION

[0050] In order to better illustrate the purpose, technical scheme and advantages of the present application, the present application will be further described through specific examples.

[0051] The specific experimental methods and equipment involved in the following examples are conventional methods or implemented according to the recommended conditions of the manufacturer's instructions unless otherwise specified; the reagents involved are commercially available unless otherwise specified.

[0052] The preparation method of g-C3N4 in the following examples is as follows: (1) adding urea into a crucible with a cover, the heating rate is 2.5 ℃ / min, heating reaction for 4 h to 550 ℃, yellow solid is obtained, and cooling to room temperature; (2) the yellow solid is further heated in an open crucible, the heating rate is 5 ℃ / min, and heating reaction for 2 h to 500 ℃, g-C3N4 is obtained.

[0053] The yield of the synthesized (E)-β-thio vinyl sulfone compound is investigated in the embodiment of the application, and the calculation method of the yield is as follows:

[0054] Yield=(actual yield / theoretical yield)*100%

[0055] Theoretical yield=total moles of raw materials injected*relative molecular mass of target product.

[0056] Example 1

[0057] Synthesis of (E)-(1-(3-methoxyphenyl)-2-tosylvinyl)(phenyl)sulfane

[0058] The structural formula of (E)-(1-(3-methoxyphenyl)-2-tosylvinyl)(phenyl)sulfane is as follows:

[0059]

[0060] S-phenyl 4-methylbenzenesulfonothioate (103.5 mg, 0.4 mmol, 2.0 equiv.), g-C3N4 (10 mg) and DMSO (2 mL) were sequentially added into a magnetically stirred Schlenk tube under argon atmosphere; then, 3-ethynylanisole (27.9 mg, 0.2 mmol, 1.0 equiv.) was added into the mixture; the mixture was stirred under irradiation of a 24 W blue LED at room temperature for 17 h. After the reaction was completed, the reaction mixture was filtered, and the precipitate was washed with ethyl acetate; the filtrate was removed by a rotary evaporator under vacuum, and finally, the residue was purified by column chromatography to obtain the product in the form of colorless oil.

[0061] The colorless oil product was subjected to 1 H NMR and 13 C NMR analysis:

[0062] 1H NMR (400 MHz, CDC13) δ: 7.52 (dd, J = 7.0, 2.1 Hz, 2H), 7.45 (d, J = 6.5 Hz, 3H), 7.29 (d, J = 8.2 Hz, 2H), 7.19 (t, J = 7.9 Hz, 1H), 7.09 (d, J = 8.0 Hz, 2H), 6.88 (dd, J = 8.3, 2.2 Hz, 1H), 6.83 (d, J = 7.5 Hz, 1H), 6.65 (s, 1H), 5.93 (s, 1H), 3.74 (s, 3H), 2.36 (s, 3H);

[0063] 13 C NMR (100 MHz, CDC13) δ: 159.1, 158.9, 143.4, 139.0, 135.4, 134.6, 130.5, 130.1, 129.1, 128.9, 128.8, 127.4, 122.8, 121.5, 115.8, 113.9, 55.15, 21.44; HRMS (ESI): m / z calcd for C 22 H 20 O3S2[M+Na] + : 419.0752, found: 419.0748.

[0064] The product was identified as:

[0065] (E)-(1-(3-Methoxyphenyl)-2-tosylvinyl)(phenyl)sulfane.

[0066] The yield of (E)-(1-(3-Methoxyphenyl)-2-tosylvinyl)(phenyl)sulfane was calculated to be 87% in this example.

[0067] Example 2

[0068] Synthesis of (E)-3-(1-(phenylthio)-2-tosylvinyl)thiophene

[0069] The structural formula of (E)-3-(1-(phenylthio)-2-tosylvinyl)thiophene is:

[0070]

[0071] S-phenyl 4-methylbenzenesulfonothioate (264.4 mg, 1.0 mmol, 5.0 equiv), g-C3N4(10 mg) and DMSO (2 mL) were added successively into a magnetically stirred oven-dried Schlenk tube under argon atmosphere; then, 3-ethynylthiophene (21.6 mg, 0.2 mmol, 1.0 equiv) was added into the mixture; the reaction mixture was stirred at room temperature under 24W blue LED irradiation for 17 h. After completion of the reaction, the reaction mixture was filtered and the precipitate was washed with ethyl acetate; the filtrate was removed under vacuum using a rotary evaporator and finally, the residue was purified using column chromatography to obtain the product as a colorless oil.

[0072] The colorless oil product was subjected to 1 H NMR and 13 C NMR analysis:

[0073] 1 H NMR (400 MHz, CDC13) δ: 7.50 - 7.42 (m, 6H), 7.33 (d, J = 8.2 Hz, 2H), 7.20 (dd, J = 5.0, 3.0 Hz, 1H), 7.12 (d, J = 8.0 Hz, 2H), 7.04 - 7.01 (m, 1H), 5.98 (s, 1H), 2.36 (s, 3H); 13 CNMR (100 MHz, CDC13) δ: 143.5, 138.9, 135.2, 133.2, 130.4, 130.1, 129.2, 128.6, 127.9, 127.2, 125.1, 123.2, 21.5; HRMS (ESI): m / z calcd for C 19 H 16 O2 S3[M+H] + : 373.0391, found: 373.0393.

[0074] The colorless oil product was determined to be (E)-3-(1-(Phenylthio)-2-tosylvinyl)thiophene.

[0075] It was calculated that the yield of (E)-3-(1-(Phenylthio)-2-tosylvinyl)thiophene in this example was 89%.

[0076] Example 3

[0077] Synthesis of (E)-Phenyl(1-tosylhex-1-en-2-yl)sulfane

[0078] The structural formula of (E)-Phenyl(1-tosylhex-1-en-2-yl)sulfane is:

[0079]

[0080] S-phenyl 4-methylbenzenesulfonothioate (106.0 mg, 0.4 mmol, 2.0 equiv.), g-C3N4(10 mg) and DMSO (2 mL) were added into a magnetically stirred oven-dried Schlenk tube under argon atmosphere; then, 1-hexyne (16.5 mg, 0.2 mmol, 1.0 equiv) was added into the mixture; the reaction mixture was stirred under irradiation of 24W blue LED at room temperature for 17 h. After the reaction was completed, the reaction mixture was filtered, and the precipitate was washed with ethyl acetate; the filtrate was removed under vacuum using a rotary evaporator, and finally, the residue was purified by column chromatography to obtain the product as colorless oil.

[0081] The colorless oil product was subjected to 1 H NMR and 13 C NMR analysis:

[0082] 1 H NMR (400 MHz, CDCl3) δ: 7.65 (d, J = 7.9 Hz, 2H), 7.41 (s, 6H), 7.28 (s, 1H), 5.53 (s, 1H), 2.78-2.71 (m, 3H), 2.40 (s, 3H), 1.36 (dd, J = 14.6, 7.3 Hz, 3H), 0.89 (t, J = 7.2 Hz, 3H);

[0083] 13 C NMR (100 MHz, CDCl3) δ: 143.7, 139.9, 135.5, 130.3, 130.0, 129.7, 128.5, 126.8, 119.6, 32.0, 32.0, 22.6, 21.5, 13.8; HRMS (ESI): m / z calcd for C 19 H 22 O2S2[M+Na] + : 369.0959, found: 369.0954.

[0084] The colorless oil product was determined to be (E)-Phenyl(1-tosylhex-1-en-2-yl)sulfane.

[0085] The yield of (E)-phenyl(l-tosylhex-l-en-2-yl)sulfane was calculated to be 88% in this example.

[0086] Example 4

[0087] Synthesis of (E)-(l-cyclohexyl-2-tosylvinyl)(phenyl)sulfane

[0088] The structural formula of (E)-(l-cyclohexyl-2-tosylvinyl)(phenyl)sulfane is:

[0089]

[0090] S-phenyl 4-methylbenzenesulfonothioate (105.9 mg, 0.4 mmol, 2.0 equiv.), g-C3N4(10 mg) and DMSO (2 mL) were added into a magnetically stirred oven-dried Schlenk tube under argon atmosphere; then, cyclohexylacetylene (23.0 mg, 0.2 mmol, 1.0 equiv) was added into the mixture; the reaction mixture was stirred at room temperature under 24W blue LED irradiation for 17 h. After the reaction was completed, the reaction mixture was filtered and the precipitate was washed with ethyl acetate; the filtrate was removed under vacuum using a rotary evaporator, and finally, the residue was purified using column chromatography to obtain the product as a colorless oil.

[0091] The colorless oil product was subjected to 1 HNMR and 13 CNMR analysis:

[0092] 1 H NMR (400 MHz, CDC13) δ: 7.66 (d, J = 7.8 Hz, 2H), 7.40 (s, 5H), 7.27 (d, J = 7.8 Hz, 2H), 5.45 (s, 1H), 3.61 (t, J = 10.9 Hz, 1H), 2.40 (s, 3H), 1.77 - 1.68 (m, 4H), 1.57 - 1.43 (m, 4H), 1.25 (d, J = 9.1 Hz, 2H);

[0093] 13C NMR (100 MHz, CDC13) δ: 169.2, 143.6, 140.3, 135.8, 130.2, 130.1, 129.6, 128.5, 126.8, 119.5, 40.9, 31.8, 26.1, 25.6, 21.5; HRMS (ESI): m / z calcd for C 21 H 24 O2S2[M+H] + : 395.1115, found: 395.1117.

[0094] The product was identified as (E)-(1-Cyclohexyl-2-tosylvinyl)(phenyl)sulfane. The yield of (E)-(1-Cyclohexyl-2-tosylvinyl)(phenyl)sulfane was calculated to be 91% in this example.

[0095] Example 5

[0096] Synthesis of (E)-(4-Chlorophenyl)(1-phenyl-2-tosylvinyl)sulfane

[0097] The structural formula of (E)-(4-Chlorophenyl)(1-phenyl-2-tosylvinyl)sulfane is:

[0098]

[0099] S-(4-chlorophenyl) 4-methylbenzenesulfonothioate (119.5 mg, 0.4 mmol, 2.0 equiv), g-C3N4(10 mg) and DMSO (2 mL) were added into a magnetically stirred oven-dried Schlenk tube under argon atmosphere, successively; then, phenylacetylene (20.4 mg, 0.2 mmol, 1.0 equiv) was added into the mixture; the reaction mixture was stirred at room temperature under irradiation of 24 W blue LED for 17 h. After completion of the reaction, the reaction mixture was filtered, and the precipitate was washed with ethyl acetate; the filtrate was removed under vacuum using a rotary evaporator, and finally, the residue was purified by column chromatography to obtain a colorless oil.

[0100] The above colorless oil was analyzed by 1 H NMR and 13 C NMR:

[0101] 1H NMR (400 MHz, CDC13) δ: 7.43 - 7.33 (m, 5H), 7.29 (d, J = 7.3 Hz, 4H), 7.20 (d, J = 7.3 Hz, 2H), 7.10 (d, J = 8.0 Hz, 2H), 5.96 (s, 1H), 2.36 (s, 3H);

[0102] 13 C NMR (100 MHz, CDC13) δ: 158.6, 143.6, 138.8, 136.9, 136.5, 133.2, 130.3, 129.6, 129.2, 129.0, 127.8, 127.3, 123.2, 21.5.

[0103] The product was determined to be: (E)-(4-Chlorophenyl)(1-phenyl-2-tosylvinyl)sulfane. The yield of (E)-(4-Chlorophenyl)(1-phenyl-2-tosylvinyl)sulfane in this example was calculated to be 94%.

[0104] Example 6

[0105] Synthesis of (E)-2-(phenylthio)-3-tosylallyl acetate

[0106] The structural formula of (E)-2-(phenylthio)-3-tosylallyl acetate is:

[0107]

[0108] S-phenyl 4-methylbenzenesulfonothioate (105.6 mg, 0.4 mmol, 2.0 equiv), g-C3N4(10 mg) and DMSO (2 mL) were added into a magnetically stirred oven-dried Schlenk tube under argon atmosphere; then, propargyl acetate (20.5 mg, 0.2 mmol, 1.0 equiv.) was added into the mixture; the reaction mixture was stirred at room temperature under irradiation of 24 W blue LED for 17 h. After completion of the reaction, the reaction mixture was filtered and the precipitate was washed with ethyl acetate; the filtrate was removed under vacuum using a rotary evaporator, and finally, the residue was purified using column chromatography to obtain a colorless oil.

[0109] The above colorless oil was subjected to H NMR and 1 H NMR and 13 C NMR analysis:

[0110] 1 H NMR (400 MHz, CDC13) δ: 7.69 (d, J = 7.8 Hz, 2H), 7.42 (s, 5H), 7.30 (d, J = 7.8 Hz, 2H), 5.52 (s, 1H), 5.39 (s, 2H), 2.42 (s, 3H), 2.13 (s, 3H);

[0111] 13 C NMR (100 MHz, CDC13) δ: 170.0, 156.8, 144.2, 138.7, 135.5, 130.6, 130.2, 129.8, 127.3, 127.0, 121.0, 60.9, 21.6, 20.6; HRMS (ESI): m / z calcd for C 18 H 18 O4S2[M+Na] + : 385.0544, found: 385.0540.

[0112] The product was identified as (E)-2-(Phenylthio)-3-tosylallylacetate. The yield of (E)-2-(Phenylthio)-3-tosylallylacetate in this example was calculated to be 79%.

[0113] Example 7

[0114] Synthesis of (1S,2R,4S)-1,7,7-Trimethylbicyclo[2.2.1]heptan-2-yl (E)-5-(phenylthio)-6- tosylhex-5-enoate

[0115] The structural formula of (1S,2R,4S)-1,7,7-Trimethylbicyclo[2.2.1]heptan-2-yl (E)-5- (phenylthio)-6-tosylhex-5-enoate is:

[0116]

[0117] S-phenyl 4-methylbenzenesulfonothioate (105.8 mg, 0.4 mmol, 2.0 equiv.), g-C3N4(10 mg) and DMSO (2 mL) were added successively into a magnetically stirred oven-dried Schlenk tube under argon atmosphere; then, 4-(chloromethyl)-2-methylphenylboronic acid (50 mg, 0.25 mmol, 1.0 equiv.) was added into the mixture.

[0118] methyl (1S,2R,4S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl hex-5-ynoate (53.2 mg, 0.2 mmol, 1.0 equiv.); the reaction mixture was stirred at room temperature under irradiation of 24W blue LED for 72 h. After completion of the reaction, the reaction mixture was filtered and the precipitate was washed with ethyl acetate; the filtrate was removed under vacuum using a rotary evaporator and finally, the residue was purified using column chromatography to obtain the product as a colorless oil.

[0119] The above colorless oil was subjected to H NMR and 1 H NMR and 13 CNMR analysis:

[0120] 1 H NMR (600 MHz, CDC13) δ: 7.59 (d, J = 8.3 Hz, 2H), 7.35 (s, 5H), 7.23 - 7.19 (m, 2H), 5.49 (s, 1H), 4.84 (ddd, J = 9.9, 3.2, 2.1 Hz, 1H), 2.81 - 2.75 (m, 2H), 2.37 - 2.33 (m, 5H), 1.95 - 1.89 (m, 3H), 1.68 (d, J = 3.5 Hz, 1H), 1.61 (t, J = 4.4 Hz, 1H), 1.55 (d, J = 6.3 Hz, 1H), 1.26 (dd, J = 8.4, 6.3 Hz, 1H), 0.92 (dd, J = 13.7, 3.4 Hz, 1H), 0.84 (s, 3H), 0.81 (s, 3H), 0.78 (s, 3H);

[0121] 13 C NMR (150 MHz, CDC13) δ: 173.2, 161.8, 143.8, 139.7, 135.5, 130.4, 130.1, 129.8, 128.3, 126.8, 120.2, 80.0, 48.7, 47.8, 44.9, 36.8, 33.9, 31.4, 28.0, 27.1, 25.1, 21.6, 19.7, 18.8, 13.6; HRMS (ESI): m / z calcd for C 29 H 36 O4S2[M+Na] + : 535.1953, found: 535.1951.

[0122] The above colorless oil was subjected to H NMR and 1 H NMR and 13 CNMR analysis, the colorless oil was identified as:

[0123] (1S,2R,4S)-1,7,7-Trimethylbicyclo[2.2.1]heptan-2-yl(E)-5-(phenylthio)-6-tosylhex-5-enoate. The yield of (1S,2R,4S)-1,7,7-Trimethylbicyclo[2.2.1]heptan-2-yl(E)-5-(phenylthio)-6-tosylhex-5-enoate in this example was 74%.

[0124] The yield of (1S,2R,4S)-1,7,7-Trimethylbicyclo[2.2.1]heptan-2-yl(E)-5-(phenylthio)-6-tosylhex-5-enoate in this example was 74%.

[0125] Comparative Example 1

[0126] The difference between this comparative example and Example 2 is that S-phenyl 4-methylbenzenesulfonothioate (106.1 mg, 0.4 mmol, 2.0 equiv.), g-C3N4 (10 mg) and DMSO (2 mL) were added sequentially to a magnetically stirred oven-dried Schlenk tube under argon; then, 3-ethynylthiophene (21.6 mg, 0.2 mmol, 1.0 equiv.) was added to the mixture; the reaction mixture was stirred at room temperature under irradiation with a 24W blue LED for 17 h. After the reaction was completed, the reaction mixture was filtered and the precipitate was washed with ethyl acetate; the filtrate was removed under vacuum using a rotary evaporator, and finally, the residue was purified using column chromatography to obtain the product as a colorless oil.

[0127] The colorless oil obtained above was subjected to 1 HNMR and 13 CNMR analysis confirmed that the colorless oil was (E)-3-(1-(Phenylthio)-2-tosylvinyl)thiophene. The yield of (E)-3-(1-(Phenylthio)-2-tosylvinyl)thiophene in this comparative example was 28%.

[0128] Comparative Example 2

[0129] This comparative example differs from Example 2 in that S-phenyl 4-methylbenzenesulfonothioate (159.2 mg, 0.6 mmol, 3.0 equiv.), g-CN (10 mg), and DMSO (2 mL) were sequentially added to an oven-dried Schlenk tube equipped with a magnetic rod under an argon atmosphere. Then, 3-ethynylthiophene (21.6 mg, 0.2 mmol, 1.0 equiv.) was added to the mixture. The reaction mixture was stirred at room temperature under 24 W blue LED illumination for 17 hours. After completion of the reaction, the reaction mixture was filtered, and the precipitate was washed with ethyl acetate. The filtrate was removed by rotary evaporation under vacuum, and the residue was purified by column chromatography to obtain a colorless oily product.

[0130] The colorless oily product was 1 HNMR and 13 CNMR analysis confirmed that the colorless oily product was (E)-3-(1-(Phenylthio)-2-tosylvinyl)thiophene. Calculation showed that the yield of (E)-3-(1-(Phenylthio)-2-tosylvinyl)thiophene in this comparative example was 39%.

[0131] Comparative Example 3

[0132] This comparative example differs from Example 2 in that S-phenyl 4-methylbenzenesulfonothioate (212.2 mg, 0.8 mmol, 4.0 equiv.), g-CN (10 mg), and DMSO (2 mL) were sequentially added to an oven-dried Schlenk tube equipped with a magnetic rod under an argon atmosphere. 3-ethynylthiophene (21.6 mg, 0.2 mmol, 1.0 equiv.) was then added to the mixture. The reaction mixture was stirred at room temperature under 24 W blue LED illumination for 17 hours. After completion of the reaction, the reaction mixture was filtered, and the precipitate was washed with ethyl acetate. The filtrate was removed by rotary evaporation under vacuum, and the residue was purified by column chromatography to obtain a colorless oily product.

[0133] The colorless oily product was 1 HNMR and 13 CNMR analysis confirmed that the colorless oily product was (E)-3-(1-(Phenylthio)-2-tosylvinyl)thiophene. Calculations showed that the yield of (E)-3-(1-(Phenylthio)-2-tosylvinyl)thiophene in this comparative example was 62%.

[0134] Comparative Example 4

[0135] The difference between this comparative example and Example 2 is that S-phenyl 4-methylbenzenesulfonothioate (318.3 mg, 1.2 mmol, 6.0 equiv.), g-C3N4(10 mg) and DMSO (2 mL) were added into a magnetically stirred oven-dried Schlenk tube under argon atmosphere sequentially; then, 3-ethynylthiophene (21.6 mg, 0.2 mmol, 1.0 equiv.) was added into the mixture; the reaction mixture was stirred under irradiation of 24W blue LED at room temperature for 17 h. After completion of the reaction, the reaction mixture was filtered and the precipitate was washed with ethyl acetate; the filtrate was removed under vacuum using a rotary evaporator, and finally, the residue was purified by column chromatography to obtain the product as a colorless oil.

[0136] The colorless oil product was subjected to 1 HNMR and 13 CNMR analysis to determine that the colorless oil product was (E)-3-(1-(Phenylthio)-2-tosylvinyl)thiophene and (Z)-3-(1-(Phenylthio)-2-tosylvinyl)thiophene

[0137] It was calculated that the yield of (E)-3-(1-(Phenylthio)-2-tosylvinyl)thiophene in this comparative example was 32%.

[0138] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and not to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A method for catalytic synthesis of (E)-β-thio vinyl sulfone compounds by using organic semiconductor carbon nitride, characterized in that, The method comprises the following steps: taking a thiosulfonate and an alkyne compound as reaction substrates, taking graphite phase carbon nitride g-C3N4 as a heterogeneous photocatalyst, reacting under the conditions of an organic solvent and light, and through filtration recrystallization or chromatographic purification to obtain the (E)-β-thio vinyl sulfone compound. The chemical equation of the reaction is as follows: Among them, R 1 Selected from aryl, heteroaryl, alkyl, alkenyl, or the acetylenic compound of formula (I) is selected from aryl acetylenic compounds, heteroaryl acetylenic compounds, C1-C 16 Straight-chain or branched alkyl acetylenic compounds, C3-C6 cycloalkyl acetylenic compounds or alkenyl acetylenic hydrocarbons; R 2 The thiosulfonate of formula (II) is selected from aryl groups, or the thiosulfonate of formula (II) is selected from aryl thiosulfonate substituted with one or more substituents, wherein the substituents are selected from methyl, methoxy, benzyloxy, and halogen groups. 2.The method of claim 1, wherein the (E) -β-thio vinyl sulfone compound is represented by the following formula 1: The organic solvent is at least one selected from dimethyl sulfoxide, ethylene glycol dimethyl ether, acetonitrile, ethyl acetate and dichloromethane. ​ 3.The method of claim 1, wherein the (E) -β-thio vinyl sulfone compound is represented by the following formula 1: The light condition is blue LED light. ​ 4. The method for catalytic synthesis of (E)-β-thio vinyl sulfone compounds by using organic semiconductor carbon nitride according to claim 3, characterized in that, Stirring is carried out under the blue LED light, and the stirring time is 17-72 h. 5.The method of claim 1, wherein the carbon nitride catalytic synthesis of organic semiconductors (E) -β-thio vinyl sulfone compounds is characterized in that, The molar ratio of the alkyne compound to the thiosulfonate is 1:(2-5).

6. The method for synthesizing (E)-β-thiovinyl sulfone compounds catalyzed by organic semiconductor carbon nitride according to claim 1, characterized in that: The molar ratio of the alkyne compound to the g-C3N4 is 1:(0.4-2.0).

7. The method for synthesizing (E)-β-thiovinyl sulfone compounds catalyzed by organic semiconductor carbon nitride according to claim 1, characterized in that: The preparation method of the g-C3N4 is as follows: (1) adding urea into a crucible with a cover, covering the crucible with the cover, heating and reacting for 3.5-4.5 h to 540-560 DEG C to obtain a yellow solid, and cooling to room temperature; (2) further heating and reacting the yellow solid in an open crucible for 1.5-2.5 h to 490-510 DEG C to obtain the g-C3N4.

8. The method for synthesizing (E)-β-thiovinyl sulfone compounds catalyzed by organic semiconductor carbon nitride according to claim 7, characterized in that: The heating rate of the heating and reaction in the step (1) is 2.5 DEG C / min, and the heating rate of the further heating and reaction in the step (2) is 5 DEG C / min.

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