Alkenyl thioester compound and preparation method thereof

Abstract

The invention discloses a preparation method of an alkenyl thioester compound, and relates to the technical field of organic synthesis, and the preparation method comprises the following steps: (1) uniformly mixing a thioacid and a 1, 1-diaryl olefin compound, and carrying out a reaction for 6-12 h at 30-150 DEG C under an illumination condition; and (2) after the reaction in the step (1) is completed, sequentially extracting, drying, distilling, separating and purifying the reaction product to obtain the alkenyl thioester compound. The preparation method breaks through the existing thioester synthesis process route, is promoted by ambient light, does not need a solvent or a catalyst, and has the characteristics of mild and green reaction conditions, wide substrate range, higher reaction efficiency, specific product configuration, simplicity and convenience in operation, safe reaction route and the like, and a representative compound has an aggregation-induced emission (AIE) property and is suitable for industrial production. Therefore, the material has potential application in the fields of photoelectric materials, biological medicines and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and in particular to an alkenyl thioester compound and a preparation method thereof. Background Art

[0002] Thioesters are a very important class of compounds that are widely found in natural compounds, drugs and bioactive molecules. Their unique structural characteristics make them widely used in medicine, biomacromolecule synthesis, functional materials and polymer polymerization, especially as acyl transfer reagents in organic synthesis reactions such as Fukuyama coupling and Liebeskind-Srogl coupling.

[0003] At present, there are many reports on the synthesis of thioester compounds. Among them, the mature processes and the main synthesis methods of thioester derivatives reported in the literature include:

[0004] 1) Thioesterification reaction of thiols / thiophenols with acylating agents: Using thiols / thiophenols and acylating agents (acyl chlorides, carboxylic acids, anhydrides, aldehydes, alcohols, gem-difluoroolefins, etc.) as raw materials, directly undergo nucleophilic acylation, oxidative acylation, thioesterification and thiocarbonylation reactions between thiols and acylating agents to obtain thioester products (Shi, Y.-J.; Sun, X.-Y.; Cao, H. et al. Thioesterification of Esters with Primary Aliphatic Thiols at Room Temperature. Chin. J. Org. Chem. 2023, doi: 10.6023 / cjoc202212008). Among them, the reaction of thiols with acylating agents (acyl chlorides, carboxylic acids, anhydrides, aldehydes) is the most classic, efficient and widely used synthesis route so far (Kazemi, M.; Shiri, L., Thioesters synthesis: recent adventures in the esterification of thiols.J.Sulfur Chem.2015,36,613-623.);

[0005] 2) Starting from carbonyl carboxylic acid and disulfide (Su, J.; Chen, A.; Zhang, G.; Jiang, Z.; Zhao, J., Photocatalytic Phosphine-Mediated Thioesterification of Carboxylic Acids with Disulfides. Org. Lett. 2023, 25, 8033-8037.) or acyl chloride and sodium sulfinate (Bogonda, G.; Patil, DV; Kim, HY; Oh, K., Visible-Light-Promoted Thiyl Radical Generation from Sodium Sulfinates: A Radical–Radical Coupling to Thioesters. Org. Lett. 2019, 21, 3774-3779.), the synthesis of thioesters is achieved under photoredox catalyst conditions;

[0006] 3) Electrochemical reductive cross-coupling of acyl chlorides and sulfinic acids toward the synthesis of thioesters. Green Chem. 2022, 24, 7350-7354.

[0007] Summarizing the existing synthesis methods of thioester compounds, it is not difficult to see that most of the existing synthesis methods of these thioester compounds are achieved under the conditions of metal, photocatalyst, oxidant or strong acid, strong base and other conditions. Therefore, there are the following problems: the use of catalysts and oxidants (strong acids, strong bases and metal salts, etc.) is required; there are few reports on the synthesis of alkenyl thioester compounds, and the current synthesis methods have high energy consumption; the current synthesis methods have harsh reaction conditions (some oxidants are cumbersome to prepare, expensive, and severely corrode equipment), cumbersome operations, difficult separation and purification, and environmental pollution.

[0008] Therefore, providing a green and efficient alkenyl thioester compound and a preparation method thereof is a technical problem that urgently needs to be solved in the art. Summary of the invention

[0009] In view of the problems existing in the prior art, the present invention proposes a green and efficient alkenyl thioester compound and a preparation method thereof. The synthesis method of the present invention has the characteristics of high functional group tolerance, a wide substrate range, mild synthesis conditions, green and high efficiency, and is expected to be applied in actual production.

[0010] In order to achieve the above object, the present invention adopts the following technical solution:

[0011] An alkenyl thioester compound, the general structural formula of the compound is:

[0012]

[0013] Wherein, R is any one of an alkyl group, an aryl group and a heteroaryl group;

[0014] R 1 is hydrogen or methyl; R 2 is monosubstituted at the 2, 3, 4 positions, or disubstituted at the 2, 4 or 3, 4 positions, and the substituted group is an electron withdrawing group (F - , Cl - Br - ,I - CF3 - 、NO2 - ), electron donating groups (Me - 、MeO - , t-Bu - ), any one of phenyl and naphthyl;

[0015] Preferably, the alkyl group is phenethyl, benzyl and cycloalkyl (C n H 2n-1 , n=3-6), the aryl group is any one of phenyl and substituted phenyl, and the heteroaryl group is any one of furyl and thienyl.

[0016] Preferably, the substituted phenyl group is monosubstituted at the 2, 3, or 4 positions, and the substituent may be an electron withdrawing group (F - , Cl - Br - ,I - CF3 - 、NO2 - ) or electron donating groups (Me - 、MeO - , t-Bu - ), any one of biphenyl and naphthyl;

[0017] The structure of the present invention is for R, R 1 and R 2 The group type (alkyl, aryl, heteroaryl), the electrical properties of the substituent (can be an electron-donating group or an electron-withdrawing group), and the position (2-, 3-, 4-position substitution) and number (mono- or di-substitution) of the substituent all show strong applicability.

[0018] Preferably, the compound is any one of the following structures:

[0019]

[0020]

[0021] A method for preparing an alkenyl thioester compound comprises the following steps:

[0022] (1) mixing the thioacid and the 1,1-diaryl olefin compound uniformly, and reacting them at 30-150° C. for 6-12 hours under light conditions;

[0023] (2) After the reaction in step (1) is completed, the reaction product is sequentially extracted, dried, distilled, and separated and purified to obtain an alkenyl thioester compound;

[0024] The synthetic route is as follows:

[0025]

[0026] The method of the invention is initiated by the charge transfer complex generated between the thioacid and the olefin compound, and the generated carbonyl thiol free radical is used to realize the transformation. The method has the characteristics of specific product stereostructure, no need for solvent and catalyst, promotion by using ambient light, and wide application range of substrates and functional groups.

[0027] Preferably, the molar ratio of the thioacid and the 1,1-diaryl olefin compound in step (1) is 1:1.

[0028] The two substrates of the present invention are both raw materials and can initiate reactions through complex action, thus avoiding the use of catalysts such as photosensitizers and transition metals in the prior art.

[0029] Preferably, the reaction temperature in step (1) is 30-150°C.

[0030] Since the temperature is mainly helpful for the subsequent production of double bonds, the reaction has a wide temperature range. Different temperatures will affect the reaction conversion rate and reaction time. The preferred temperature is 80-120°C.

[0031] Preferably, the thioacid in step (1) is a thioacid substituted with an alkyl, aryl or heteroaryl group.

[0032] The method of the present invention has a wide application range for substrate thioacids, breaking through the limitation of the prior art that the sulfur source can generally only be thiophenol or thiol.

[0033] Preferably, the 1,1-diaryl olefin compound in step (1) is a 1,1-disubstituted aryl olefin.

[0034] The method of the present invention has a wide application range for substrate 1,1-diaryl olefin compounds, breaking through the limitation of the prior art that generally only alkyl thioesters can be produced by reacting with olefins.

[0035] Preferably, the reaction system in step (1) is solvent-free or solvent-containing.

[0036] The method can be carried out in the absence of solvent or with solvent, preferably in the absence of solvent, breaking through the constraints of the prior art that the reaction can only be carried out in a solvent system, and the reaction environment is more environmentally friendly. If the method is carried out in the presence of solvent, the preferred solvent is any one of ethanol, tetrahydrofuran acetonitrile, dichloromethane and ethyl acetate, and the reaction concentration is 0.5M.

[0037] Preferably, the illumination in step (1) is any one of sunlight, ambient light, household energy-saving lamp, blue LED, white LED and green LED.

[0038] The presence of light can promote reaction conversion. This method has a wide range of applicability to light sources. The preferred light source is ambient light, which avoids the requirement of the prior art for special light source equipment.

[0039] Preferably, the extraction in step (2) is performed using dichloromethane or ethyl acetate;

[0040] The separation and purification adopts silica gel column chromatography.

[0041] Application of an alkenyl thioester compound as described above or an alkenyl thioester compound prepared by the preparation method as described above in optoelectronic materials and biomedicine.

[0042] Compared with the prior art, the present invention has the following beneficial effects:

[0043] The preparation method of the present invention breaks the existing process route for synthesizing thioesters. It is promoted by ambient light and does not require solvents and catalysts. It has the characteristics of mild and green reaction conditions, a wide substrate range, high reaction efficiency, specific product configuration, simple operation, and a safe reaction route. In addition, representative compounds have aggregation-induced emission (AIE) properties, indicating that they have potential applications in optoelectronic materials, biomedicine and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. The drawings in this description are only embodiments of the present invention.

[0045] Figure 1 This is a diagram showing the application of the alkenyl thioester compounds of the present invention as key intermediates in many fields;

[0046] Figure 2 The single crystal structure diagram of (Z)-S-(2-phenyl-2-(p-tolyl))vinyl)benzene sulfate prepared in Example 10 of the present invention;

[0047] Figure 3 The relative emission intensity diagram of 1,1-diphenylvinyl p-nitrobenzoyl thioester (preparation method is the same as Example 1) of the present invention in THF / H2O mixed solutions with different ratios, luminescent photos of solutions with different ratios, and a maximum emission intensity change curve diagram. DETAILED DESCRIPTION

[0048] Embodiments of the present invention are described below. Examples of the embodiments are shown in the accompanying drawings. The embodiments described with reference to the accompanying drawings are exemplary and are intended to be used to explain the present invention, but are not to be construed as limiting the present invention.

[0049] Example 1

[0050] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0051] (1) Thiobenzoic acid (1 mmol) and 1,1-diphenylethylene (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100° C. in an oil bath, and reacted for 6 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by distillation under reduced pressure to obtain a crude product.

[0052] (2) The crude product was chromatographed on a silica gel column (300-400 mesh, Qingdao Ocean Chemical Co., Ltd.) and eluted with an eluent (petroleum ether: dichloromethane = 6:1 (V:V)) to obtain a white solid, which was the product 1,1-diphenylvinyl benzoyl thioester, with a yield of 85%, a melting point of 107-108° C., and a structural formula as follows:

[0053]

[0054] 1 H NMR (400MHz, CDCl3) δ7.93 (d, J=7.8Hz, 2H), 7.55 (t, J=7.4Hz, 2H), 7.42 (dt, J1=7 .5Hz,J2=4.0Hz,4H),7.37(d,J=4.6Hz,2H),7.34(t,J=7.78Hz,5H),7.28(s,1H);

[0055] 13C NMR (100MHz, CDCl3) δ188.3,142.9,141.0,139.8,136.6,133.7,129.5,128.7,128.5,128.4,128.1,127.9,127.5,127.4,116.5;

[0056] HRMS(ESI)(m / z):Calcd for C 21 H 16 OS(M+H) + :317.1000, found 317.1003.

[0057] Example 2

[0058] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0059] (1) 4-Methylthiobenzoic acid (1 mmol) and 1,1-diphenylethylene (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100° C. in an oil bath, and reacted for 6 h under ambient light. The reaction was monitored by TLC until the reaction was complete. The reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by vacuum distillation to obtain a crude product.

[0060] (2) The crude product was chromatographed on a silica gel column (300-400 mesh, Qingdao Ocean Chemical Co., Ltd.) and eluted with an eluent (petroleum ether: dichloromethane = 6:1 (V:V)) to obtain a white solid, which was the product 1,1-diphenylvinyl 4-methylbenzoyl thioester, with a yield of 80%, a melting point of 105-106° C., and a structural formula as follows:

[0061]

[0062] 1 H NMR (400MHz, CDCl3) δ7.83 (d, J=8.3Hz, 2H), 7.55 (s, 1H), 7.40 (td, J1=12Hz, J2=6. 8Hz,3H),7.31(t,J=7.0Hz,6H),7.25(d,J=21.3Hz,2H),7.20(s,1H),2.38(s,3H);

[0063] 13 C NMR (100MHz, CDCl3) δ187.8,144.6,142.6,141.0,139.9,134.1,129.5,129.4,128.5,128.3,128.0,127.8,127.5,127.4,116.8,21.7;

[0064] HRMS(ESI)(m / z):Calcd for C 22 H 18 OS(M+H) + :331.1157, found 331.1159.

[0065] Example 3

[0066] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0067] (1) 4-Methoxythiobenzoic acid (1 mmol) and 1,1-diphenylethylene (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100° C. in an oil bath, and reacted for 7 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by vacuum distillation to obtain a crude product.

[0068] (2) The crude product was chromatographed on a silica gel column (300-400 mesh, Qingdao Ocean Chemical Co., Ltd.) and eluted with an eluent (petroleum ether: dichloromethane = 5:1 (V:V)) to obtain a white solid, which was the product 1,1-diphenylvinyl 4-methoxybenzoyl thioester, with a yield of 75%, a melting point of 110-111° C., and a structural formula as follows:

[0069]

[0070] 1 H NMR (400MHz, CDCl3) δ7.91 (d, J=8.9Hz, 2H), 7.54 (s, 1H), 7.41 (td, J1=14.0Hz, J2=6.7Hz, 3H), 7.32(d,J=5.5Hz,3H),7.29(d,J=5.6Hz,2H),7.26(s,1H),6.89(d,J=8.9Hz,2H),3.83(s,3H);

[0071] 13 C NMR (100MHz, CDCl3) δ186.7,164.0,142.3,141.1,139.9,129.6,129.5,129.4,128.5,128.3,128.0,127.7,127.5,117.0,113.9,55.5;

[0072] HRMS(ESI)(m / z):Calcd for C 22 H 18 O2S(M+H) +:347.1106, found 347.1104.

[0073] Example 4

[0074] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0075] (1) 2-Chlorothiobenzoic acid (1 mmol) and 1,1-diphenylethylene (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100° C. in an oil bath, and reacted for 8 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by distillation under reduced pressure to obtain a crude product;

[0076] (2) The crude product was chromatographed on a silica gel column (300-400 mesh, Qingdao Ocean Chemical Co., Ltd.) and eluted with an eluent (petroleum ether: dichloromethane = 5:1 (V:V)) to obtain a light yellow solid, which was the product 1,1-diphenylvinyl 2-chlorobenzoyl thioester, with a yield of 51%, a melting point of 108-109° C., and a structural formula as follows:

[0077]

[0078] 1 H NMR (400MHz, CDCl3) δ7.49 (d, J=7.8Hz, 1H), 7.40 (s, 1H), 7.31 (dd, J1=7.3Hz, J2=2.6Hz ,2H),7.25(d,J=5.5Hz,2H),7.22(d,J=9.0Hz,4H),7.18(d,J=8.8Hz,4H),7.13(s,1H);

[0079] 13 C NMR (100MHz, CDCl3) δ188.2,143.5,140.7,139.5,136.9,132.6,131.2,131.0, 129.5,129.2,128.7,128.6,128.4,128.3,128.1,128.0,127.6,126.8,116.4;

[0080] HRMS(ESI)(m / z):Calcd for C 21 H 15 ClOS(M+H) + :351.0610, found 351.0612.

[0081] Example 5

[0082] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0083] (1) 3-Chlorothiobenzoic acid (1 mmol) and 1,1-diphenylethylene (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100° C. in an oil bath, and reacted for 8 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by vacuum distillation to obtain a crude product.

[0084] (2) The crude product was chromatographed on a silica gel column (300-400 mesh, Qingdao Ocean Chemical Co., Ltd.) and eluted with an eluent (petroleum ether: dichloromethane = 6:1 (V:V)) to obtain a light yellow solid, which was the product 1,1-diphenylvinyl 3-chlorobenzoyl thioester, with a yield of 70%, a melting point of 113-114° C., and a structural formula as follows:

[0085]

[0086] 1 H NMR (400MHz, CDCl3) δ7.84 (d, J = 8.4Hz, 2H), 7.50 (s, 1H), 7.41 (t, J = 6.5Hz, 2H), 7.35 (dd, J1 = 17.3Hz, J2 = 8.9Hz, 5H), 7.29 (d, J = 4.0Hz, 4H), 7.27 (s, 1H);

[0087] 13 C NMR (100MHz, CDCl3) δ187.2,143.6,140.8,139.6,138.2,135.0,133.5,130.0,129.5,128.6,128.4,128.3,128.0,127.5,127.3,125.4,115.8;

[0088] HRMS(ESI)(m / z):CalcdforC 21 H 15 ClOS(M+H) + :351.0610, found 351.0613.

[0089] Example 6

[0090] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0091] (1) Naphthothioic acid (1 mmol) and 1,1-diphenylethylene (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100° C. in an oil bath, and reacted for 7 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by distillation under reduced pressure to obtain a crude product.

[0092] (2) The crude product was chromatographed on a silica gel column (300-400 mesh, Qingdao Ocean Chemical Co., Ltd.) and eluted with an eluent (petroleum ether: dichloromethane = 5:1 (V:V)) to obtain a white solid, which was the product 1,1-diphenylvinyl naphthioyl thioester, with a yield of 65%, a melting point of 118-119° C., and a structural formula as follows:

[0093]

[0094] 1 H NMR(400MHz, CDCl3)δ8.47(s,1H),8.00-7.80(m,5H),7.61(s,1H),7.53(td,J1 =14.72, J2=7Hz,3H),7.43(d,J=7.5Hz,2H),7.34(d,J=9.9Hz,5H),7.30(s,1H);

[0095] 13 C NMR (100MHz, CDCl3) δ188.1,142.9,141.0,139.9,135.9,133.9,132.4,129.6, 128.9,128.7,128.6,128.4,128.2,127.9,127.8,127.6,127.0,123.1,116.7;

[0096] HRMS(ESI)(m / z):Calcd for C 25 H 18 OS(M+H) + :367.1157, found 367.1159.

[0097] Example 7

[0098] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0099] (1) Thiothiophenecarboxylic acid (1 mmol) and 1,1-diphenylethylene (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100° C. in an oil bath, and reacted for 8 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by distillation under reduced pressure to obtain a crude product;

[0100] (2) The crude product was chromatographed on a silica gel column (300-400 mesh, Qingdao Ocean Chemical Co., Ltd.) and eluted with an eluent (petroleum ether: dichloromethane = 6:1 (V:V)) to obtain a light yellow solid, which was the product 1,1-diphenylvinylthiophenecarbonyl thioester, with a yield of 65%, a melting point of 103-104° C., and a structural formula as follows:

[0101]

[0102] 1 H NMR (400MHz, CDCl3) δ7.74(d,J=3.9Hz,1H),7.61(d,J=4.9Hz,1H),7.47(s,1H),7.41(t d, J1=14.3Hz, J2=6.7Hz, 3H), 7.31 (t, J=2.2Hz, 6H), 7.29 (s, 1H), 7.07 (t, J=4.5Hz, 1H);

[0103] 13 C NMR (100MHz, CDCl3) δ180.4,142.8,141.6,140.9,139.7,133.2,131.4,129.5,128.6,128.4,128.2,128.0,127.9,127.5,115.9;

[0104] HRMS(ESI)(m / z):Calcd for C 19 H 14 OS2(M+H) + :323.0564, found 323.0567.

[0105] Example 8

[0106] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0107] (1) Thiobenzylcarboxylic acid (1 mmol) and 1,1-diphenylethylene (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100° C. in an oil bath, and reacted for 7 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by distillation under reduced pressure to obtain a crude product.

[0108] (2) The crude product was chromatographed on a silica gel column (300-400 mesh, Qingdao Ocean Chemical Co., Ltd.) and eluted with an eluent (petroleum ether: dichloromethane = 6:1 (V:V)) to obtain a light yellow solid, which was the product 1,1-diphenylvinyl benzyl thioester, with a yield of 66%, a melting point of 102-103° C., and the structural formula was as follows:

[0109]

[0110] 1 H NMR (400MHz, CDCl3) δ7.28 (d, J = 38.5Hz, 15H), 7.15 (s, 1H), 3.77 (s, 2H);

[0111] 13 C NMR (100MHz, CDCl3) δ193.50,142.77,140.93,139.70,133.30,129.68,129. 54,128.85,128.78,128.59,128.46,128.23,128.00,127.61,116.54,50.64;

[0112] HRMS(ESI)(m / z):Calcd for C 22 H 18 OS(M+H) + :331.1157, found 331.1160.

[0113] Example 9

[0114] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0115] (1) Cyclothiopropylcarboxylic acid (1 mmol) and 1,1-diphenylethylene (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100°C in an oil bath, and reacted for 6 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by distillation under reduced pressure to obtain a crude product.

[0116] (2) The crude product was chromatographed on a silica gel column (300-400 mesh, Qingdao Ocean Chemical Co., Ltd.) and eluted with an eluent (petroleum ether: dichloromethane = 7:1 (V:V)) to obtain a light yellow solid, which was the product 1,1-diphenylvinyl cyclopropyl thioester, with a yield of 67%, a melting point of 103-104° C., and a structural formula as follows:

[0117]

[0118] 1 H NMR (400MHz, CDCl3) δ7.38(t,J=7.2Hz,2H),7.34(s,1H),7.32(s,1H),7.26(dd,J1=7.5Hz,J2=2.5Hz,6H),7.24(s ,1H),2.32(td,J1=20.1Hz,J2=3.6Hz,1H),2.17(td,J1=8.7Hz,J2=4.2Hz,1H),1.91(td,J1=7.7Hz,J2=4.4Hz,1H);

[0119] 13 C NMR (100MHz, CDCl3) δ193.50,142.77,140.93,139.70,133.30,129.68,129. 54,128.85,128.78,128.59,128.46,128.23,128.00,127.61,116.54,50.64;

[0120] HRMS(ESI)(m / z):Calcd for C 18 H 16 OS(M+H) + :281.1000,found 281.1004.

[0121] Example 10

[0122] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0123] (1) Thiobenzoic acid (1 mmol) and 1-methyl-4-(1-phenylvinyl)benzene (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100° C. in an oil bath, and reacted for 7 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by distillation under reduced pressure to obtain a crude product;

[0124] (2) The crude product was chromatographed on a silica gel column (Qingdao Ocean Chemical Co., Ltd., 300-400 mesh) using an eluent (petroleum ether: dichloromethane = 6:1 (V:V)) to obtain a white solid, which is the product (Z)-S-(2-phenyl-2-(p-tolyl))vinyl)benzene sulfate. Figure 2 The single crystal structure of the product is shown in FIG. 1 , with a yield of 77%, a melting point of 111-112°C, and a structural formula as follows:

[0125]

[0126] 1 H NMR (400MHz, CDCl3) δ7.93(d,J=7.6Hz,2H),7.54(t,J=7.6Hz,1H),7.42(d,J=7.5Hz,2H),7.34(s,2H),7.30(d,J=7.1Hz,3H),7.22(s,2H),2.40(s,3H);

[0127] 13 C NMR (10MHz, CDCl3) δ188.46,143.06,141.23,137.96,136.76,133.65,129.47,129.25,128.72,128.36,127.87,127.63,127.39,116.18,21.42;

[0128] HRMS(ESI)(m / z):Calcd for C 22 H 18 OS(M+H) + :331.1157, found 331.1159.

[0129] Embodiment 11

[0130] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0131] (1) Thiobenzoic acid (1 mmol) and 1-methoxy-4-(1-phenylvinyl)benzene (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100° C. in an oil bath, and reacted for 8 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by distillation under reduced pressure to obtain a crude product;

[0132] (2) The crude product was chromatographed on a silica gel column (Qingdao Ocean Chemical Co., Ltd., 300-400 mesh) and eluted with an eluent (petroleum ether: dichloromethane = 6:1 (V:V)) to obtain a white solid, i.e., the product (Z)-S-(2-phenyl-2-(p-methoxyphenyl))vinyl)benzene sulfate, with a yield of 69%, a melting point of 112-113° C., and the structural formula is as follows:

[0133]

[0134] 1 H NMR (400MHz, CDCl3) δ7.95 (d, J = 7.7Hz, 2H), 7.55 (d, J = 7.8Hz, 1H), 7.44 (dd, J1 = 12.9Hz, J2 = 5. 4Hz,3H),7.31(d,J=8.5Hz,4H),7.25(s,2H),7.23(s,1H),6.95(d,J=8.3Hz,2H),3.86(s,3H);

[0135] 13 C NMR (100MHz, CDCl3) δ188.5,159.4,142.8,141.3,136.7,133.6,132.1,130.8,128.7,128.3,127.6,127.3,115.9,113.8,55.2;

[0136] HRMS(ESI)(m / z):Calcd for C 22 H 18 O2S(M+H) + :347.1106, found 347.1108.

[0137] Example 12

[0138] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0139] (1) Thiobenzoic acid (1 mmol) and 1-fluoro-4-(1-phenylvinyl)benzene (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100° C. in an oil bath, and reacted for 8 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by distillation under reduced pressure to obtain a crude product;

[0140] (2) The crude product was chromatographed on a silica gel column (Qingdao Ocean Chemical Co., Ltd., 300-400 mesh) using an eluent (petroleum ether: dichloromethane = 6:1 (V:V)) to obtain a white solid, i.e., the product (Z)-S-(2-phenyl-2-(p-fluorophenyl))vinyl)benzene sulfate, with a yield of 75%, a melting point of 109-110° C., and the structural formula is as follows:

[0141]

[0142] 1 H NMR (400MHz, CDCl3) δ7.91 (dd, J1=4.8Hz, J2=7.0Hz, 2H), 7.53 (s, 1H), 7.47 (s, 1H), 7.39 (d, J= 7.5Hz,3H),7.28(dd,J1=15.5Hz,J2=7.2Hz,6H),7.10(t,J=8.7Hz,1H),6.98(t,J=8.7Hz,1H);

[0143] 13 C NMR (100MHz, CDCl3) δ188.2,188.0,163.,163.7,161.4,161.2,141.9,141.9,140.8,139.7,137.2,137.2,136.6,136.6, 135.8,135.7,133.8,133.7,131.4,131.3,129.5,129.3,129.2,128.8,128.7,128.6,128.5,128.3,128.1,127.5,127.4;

[0144] 19 F NMR (376MHz, CDCl3) δ-113.9 (s, 1F);

[0145] HRMS(ESI)(m / z):Calcd for C 21 H 15 FOS(M+H) + :335.0906, found 335.0910.

[0146] Example 13

[0147] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0148] (1) Thiobenzoic acid (1 mmol) and 1-bromo-4-(1-phenylvinyl)benzene (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100° C. in an oil bath, and reacted for 8 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by distillation under reduced pressure to obtain a crude product.

[0149] (2) The crude product was chromatographed on a silica gel column (Qingdao Ocean Chemical Co., Ltd., 300-400 mesh) and eluted with an eluent (petroleum ether: dichloromethane = 6:1 (V:V)) to obtain a white solid, i.e., the product (Z)-S-(2-phenyl-2-(p-bromophenyl))vinyl)benzene sulfate, with a yield of 73%, a melting point of 112-113° C., and the structural formula is as follows:

[0150]

[0151] 1 H NMR (400MHz, CDCl3) δ7.91(t,J=6.4Hz,2H),7.53(d,J=8.5Hz,3H),7.38(t,J=7.8Hz,4H),7.26(t,J=11.4Hz,4H),7.18(s,1H),7.15(s,1H);

[0152] 13 C NMR (100MHz, CDCl3) δ187.85,141.79,1415,138.76,136.56,133.82,131.85,131.57,131.32,129.51,128.82,128.54,127.45,122.32,117.25;

[0153] HRMS(ESI)(m / z):Calcd for C 21 H 15 BrOS(M+H) + :395.0105, found 395.0108.

[0154] Embodiment 14

[0155] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0156] (1) Thiobenzoic acid (1 mmol) and 1-methyl-2-(1-phenylvinyl)benzene (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100° C. in an oil bath, and reacted for 8 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by distillation under reduced pressure to obtain a crude product;

[0157] (2) The crude product was chromatographed on a silica gel column (Qingdao Ocean Chemical Co., Ltd., 300-400 mesh) and eluted with an eluent (petroleum ether: dichloromethane = 6:1 (V:V)) to obtain a white solid, i.e., the product (Z)-S-(2-phenyl-2-(o-tolyl))vinyl)benzene sulfate, with a yield of 70%, a melting point of 115-116° C., and the structural formula is as follows:

[0158]

[0159] 1 H NMR (400MHz, CDCl3) δ7.87(d,J=7.7Hz,2H),7.73(s,1H),7.47(t,J=7.1Hz,2H),7. 36(s,1H),7.29(d,J=12.3Hz,6H),7.22(s,1H),7.16(d,J=7.8Hz,2H),2.10(s,3H);

[0160] 13 C NMR (100MHz, CDCl3) δ188.23,141.96,139.34,139.07,136.71,136.33,133. 75,130.64,129.67,128.78,128.68,128.41,127.48,126.34,117.18,19.58;

[0161] HRMS(ESI)(m / z):Calcd for C 22 H 18 OS(M+H) + :331.1157, found 331.1159.

[0162] Embodiment 15

[0163] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0164] (1) Thiobenzoic acid (1 mmol) and 1-methyl-3-(1-phenylvinyl)benzene (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100° C. in an oil bath, and reacted for 9 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by distillation under reduced pressure to obtain a crude product;

[0165] (2) The crude product was chromatographed on a silica gel column (Qingdao Ocean Chemical Co., Ltd., 300-400 mesh) and eluted with an eluent (petroleum ether: dichloromethane = 6:1 (V:V)) to obtain a white solid, i.e., the product (Z)-S-(2-phenyl-2-(m-tolyl))vinyl)benzene sulfate, with a yield of 68%, a melting point of 113-114° C., and the structural formula is as follows:

[0166]

[0167] 1 H NMR (400MHz, CDCl3) δ7.93 (d, J = 8.0 Hz, 2H), 7.53 (t, J = 8.0 Hz, 2H), 7.41 (d, J = 4.5 Hz, 2H), 7.36 (d, J = 19. 3Hz,3H),7.30(d,J=7.3Hz,3H),7.20(t,J=8.8Hz,2H),7.11(s,1H),7.09(s,1H),2.35(d,J=15.2Hz,3H);

[0168] 13 C NMR (100MHz, CDCl3) δ188.43,141.01,139.97,138.02,136.74,133.68,129. 57,128.74,128.54,128.39,127.55,127.39,126.65,124.86,116.41,21.51;

[0169] HRMS(ESI)(m / z):Calcd for C 22 H 18 OS(M+H) + :331.1157, found 331.1156.

[0170] Example 16

[0171] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0172] (1) Thiobenzoic acid (1 mmol) and 1,2-dichloro-4-(1-phenylvinyl)benzene (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100° C. in an oil bath, and reacted for 9 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by distillation under reduced pressure to obtain a crude product;

[0173] (2) The crude product was chromatographed on a silica gel column (300-400 mesh, Qingdao Ocean Chemical Co., Ltd.) and eluted with an eluent (petroleum ether: dichloromethane = 6:1 (V:V)) to obtain a light yellow solid, i.e., the product (Z)-S-(2-(3,4-dichlorophenyl))-2-phenylvinyl)benzene sulfate, with a yield of 63%, a melting point of 115-116° C., and the structural formula is as follows:

[0174]

[0175] 1 H NMR (400MHz, CDCl3) δ7.89(t,J=8.8Hz,2H),7.56(d,J=2.4Hz,1H),7.49(dd,J1=7.1Hz,J2=12.8Hz,2H),7.40(s,1H), 7.37(t,J=7.1Hz,3H),7.56(d,J=8.2Hz,2H),7.28(s,2H),7.24(d,J=8.3Hz,1H),7.11(td,J1=4.7Hz,J2=2.0Hz,1H);

[0176] 13 C NMR (100MHz, CDCl3) δ187.36,141.02,140.47,140.14,139.88,138.90,136.39,134.0 1,131.50,130.73,130.35,129.46,128.85,128.69,127.47,126.74,118.89,118.24;

[0177] HRMS(ESI)(m / z):CalcdforC 21 H 14 Cl2OS(M+H) + :385.0221,found385.0223.

[0178] Embodiment 17

[0179] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0180] (1) Thiobenzoic acid (1 mmol) and 1-bromo-4-(1-(p-methylphenyl)vinyl)benzene (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100° C. in an oil bath, and reacted for 9 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by distillation under reduced pressure to obtain a crude product.

[0181] (2) The crude product was chromatographed on a silica gel column (Qingdao Ocean Chemical Co., Ltd., 300-400 mesh) and eluted with an eluent (petroleum ether: dichloromethane = 6:1 (V:V)) to obtain a light yellow solid, i.e., the product (Z)-S-(2-(4-bromophenyl)-2-(p-tolyl)vinyl)benzene sulfate, with a yield of 75%, a melting point of 117-118° C., and the structural formula is as follows:

[0182]

[0183] 1 H NMR (400MHz, CDCl3) δ7.93(d,J=7.8Hz,2H),7.55(d,J=8.4Hz,2H),7.48(s,1H),7.43(d,J=6.2Hz, 3H),7.23(d,J=12.4Hz,3H),7.19(d,J=3.5Hz,2H),7.13(d,J=8.2Hz,1H),2.38(d,J=22.2Hz,3H);

[0184] 13 C NMR (100MHz, CDCl3) δ188.1,140.1,138.9,137.7,136.6,133.8,131.8,131.5,131.3,129.3,129.2,128.8,127.4,122.2,116.1,21.2;

[0185] HRMS(ESI)(m / z):Calcd for C 22 H 17 BrOS(M+H) + :409.0262,found 409.0265.

[0186] Embodiment 18

[0187] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0188] (1) Thiobenzoic acid (1 mmol) and 1-(1-phenylvinyl)naphthalene (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100° C. in an oil bath, and reacted for 8 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by distillation under reduced pressure to obtain a crude product;

[0189] (2) The crude product was chromatographed on a silica gel column (Qingdao Ocean Chemical Co., Ltd., 300-400 mesh) and eluted with an eluent (petroleum ether: dichloromethane = 6:1 (V:V)) to obtain a white solid, i.e., the product (Z)-S-(2-(naphthalen-1-yl))-2-phenylvinyl)benzene sulfate, with a yield of 66%, a melting point of 120-121° C., and the structural formula is as follows:

[0190]

[0191] 1 H NMR (400MHz, CDCl3) δ7.89(d,J=7.5Hz,1H),7.84(d,J=13.7Hz,1H),7.80(s,1H),7.72(dd,J1=13.5Hz,J2=8.2Hz,2H),7.44(d,J=8 .4Hz,1H),7.38(d,J=7.3Hz,2H),7.32(d,J=7.3Hz,4H),7.27(s,1H),7.23(d,J=6.7Hz,2H),7.21(s,1H),7.18(s,1H),7.15(s,1H);

[0192] 13 C NMR (100MHz, CDCl3) δ188.2,142.1,136.8,134.0,133.8,133.7,131.9,128.8,128.7,128.6, 128.5,128.4,128.0,128.0,127.5,127.3,126.4,126.3,126.2,126.2,125.8,118.9,118.8;

[0193] HRMS(ESI)(m / z):Calcd for C 25 H 18 OS(M+H) + :367.1157, found 367.1160.

[0194] Embodiment 19

[0195] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0196] (1) Thiobenzoic acid (1 mmol) and 4-(1-phenylvinyl)-1,1'-biphenyl (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100° C. in an oil bath, and reacted for 7 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by distillation under reduced pressure to obtain a crude product;

[0197] (2) The crude product was chromatographed on a silica gel column (300-400 mesh, Qingdao Ocean Chemical Co., Ltd.) and eluted with an eluent (petroleum ether: dichloromethane = 6:1 (V:V)) to obtain a white solid, namely the product (Z)-S-(2-([1,1'-biphenyl]-4-yl))-2-phenylvinyl)benzene sulfate, with a yield of 68%, a melting point of 111-112° C., and the structural formula is as follows:

[0198]

[0199] 1 H NMR (400MHz, CDCl3) δ7.96(d,J=7.2Hz,2H),7.66(d,J=8.4Hz,3H),7.60(t,J=7.0Hz,1H),7.56(d,J=6.6Hz,2H),7.46( dd,J1=10.7Hz,J2=7.6Hz,4H),7.42(s,1H),7.49(dd,J1=7.1Hz,J2=12.8Hz,3H),7.49(d,J=15.7Hz,2H),7.33(s,1H);

[0200] 13 C NMR (100MHz, CDCl3) δ188.3,142.7,141.1,140.9,140.6,138.8,136.7,133.7,130.0,128.9,128.7,128.4,127.7,127.4,127.2,127.1,116.6;

[0201] HRMS(ESI)(m / z):Calcd for C 27 H 20 OS(M+H) + :393.1313, found 393.1315.

[0202] Embodiment 20

[0203] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0204] (1) Place p-fluorothiobenzoic acid (1 mmol) and 1,1-diphenylethylene (1 mmol) in a 25 mL round-bottom flask, heat to 100° C. in an oil bath, and react for 8 h under ambient light. Monitor by TLC until the reaction is complete. Pour the reaction solution into water, extract with dichloromethane three times, combine the organic phases, dry, and remove the organic solvent by distillation under reduced pressure to obtain a crude product.

[0205] (2) The crude product was chromatographed on a silica gel column (300-400 mesh, Qingdao Ocean Chemical Co., Ltd.) and eluted with an eluent (petroleum ether: dichloromethane = 6:1 (V:V)) to obtain a white solid, which was the product 1,1-diphenylvinyl 4-fluorobenzoyl thioester, with a yield of 78% and a melting point of 119-120° C. The structural formula is as follows:

[0206]

[0207] 1 HNMR (400MHz, CDCl3) δ7.93 (dd, J1=5.4Hz, J2=9.0Hz, 2H), 7.51 (s, 1H), 7.39 (dd, J1=7.1Hz, J2=1 2.2Hz,4H),7.32(s,2H),7.93(dd,J1=1.8Hz,J2=3.4Hz,3H),7.28(s,1H),7.07(t,J=8.7Hz,2H);

[0208] 13 C NMR (100MHz, CDCl3) δ186.8,167.3,164.8,143.2,140.9,139.8,133.0,130 .0,129.9,129.5,128.6,128.4,128.2,128.0,127.5,116.2,116.0,115.8;

[0209] 19 F NMR (376MHz, CDCl3) δ-103.82 (s, 1F);

[0210] HRMS(ESI)(m / z):Calcd for C 21 H 15 FOS(M+H) + :335.0906, found 335.0908.

[0211] Embodiment 21

[0212] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0213] (1) p-Iodothiobenzoic acid (1 mmol) and 1,1-diphenylethylene (1 mmol) were placed in a 25 mL round-bottom flask, heated to 100° C. in an oil bath, and reacted for 7 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane three times. The organic phases were combined, dried, and the organic solvent was removed by distillation under reduced pressure to obtain a crude product;

[0214] (2) The crude product was chromatographed on a silica gel column (300-400 mesh, Qingdao Ocean Chemical Co., Ltd.) and eluted with an eluent (petroleum ether: dichloromethane = 6:1 (V:V)) to obtain a white solid, which was the product 1,1-diphenylvinyl 4-fluorobenzoyl thioester, with a yield of 61% and a melting point of 135-136° C. The structural formula is as follows:

[0215]

[0216] 1 H NMR (400MHz, CDCl3) δ7.78(d,J=8.7Hz,2H),7.63(d,J=8.5Hz,2H),7.49(s,1H),7. 41(dd,J1=6.5Hz,J2=13.6Hz,3H),7.32(d,J=2.4Hz,4H),7.30(s,2H),7.28(s,1H);

[0217] 13 C NMR (100MHz, CDCl3) δ187.7,143.4,140.8,139.7,138.0,135.9,129.5,128.6,128.5,128.4,128.2,128.0,127.5,115.9,101.5;

[0218] HRMS(ESI)(m / z):Calcd for C 21 H 15 IOS(M+H) + :442.9967,found 442.969.

[0219] Embodiment 22

[0220] The present invention provides an alkenyl thioester compound, and the preparation method specifically comprises the following steps:

[0221] (1) Thiobenzoic acid (1 mmol) and 1,1-diphenylethylene (1 mmol) were placed in a 25 mL round-bottom flask, and 2 mL of ethyl acetate was added. The mixture was heated to 100° C. in an oil bath and reacted for 6 h under ambient light. After TLC monitoring until the reaction was complete, the reaction solution was poured into water and extracted with dichloromethane for 3 times. The organic phases were combined, dried, and the organic solvent was removed by distillation under reduced pressure to obtain a crude product.

[0222] (2) The crude product was chromatographed on a silica gel column (300-400 mesh, Qingdao Ocean Chemical Co., Ltd.) and eluted with an eluent (petroleum ether: dichloromethane = 6:1 (V:V)) to obtain a white solid, which was the product 1,1-diphenylvinyl benzoyl thioester, with a yield of 85%, a melting point of 107-108° C., and a structural formula as follows:

[0223]

[0224] 1 H NMR (400MHz, CDCl3) δ7.93 (d, J=7.8Hz, 2H), 7.55 (t, J=7.4Hz, 2H), 7.42 (dt, J1=7 .5Hz,J2=4.0Hz,4H),7.37(d,J=4.6Hz,2H),7.34(t,J=7.78Hz,5H),7.28(s,1H);

[0225] 13 C NMR (100MHz, CDCl3) δ188.3,142.9,141.0,139.8,136.6,133.7,129.5,128.7,128.5,128.4,128.1,127.9,127.5,127.4,116.5;

[0226] HRMS(ESI)(m / z):Calcd for C 21 H 16 OS(M+H) + :317.1000, found 317.1003.

[0227] According to literature reports, alkenyl thioester fragments are widely present in drugs, natural products, etc., such as Figure 1 shown.

[0228] The method for synthesizing alkenyl thioesters provided by the present invention breaks the existing synthetic process route, does not require solvents and catalysts, has a specific product stereostructure, has a wide substrate application range, and can obtain alkenyl thioester compounds with different substituents.

[0229] In addition, according to Figure 3Information is provided. The left figure shows the relative emission intensity of the product 1,1-diphenylvinyl p-nitrobenzoyl thioester (preparation method is the same as Example 1) in different proportions of THF / H2O mixed solutions. The right figure shows the luminescence photos of solutions with different proportions and the maximum emission intensity change curve. The results show that the emission intensity increases significantly with the increase of water content, showing a typical aggregation-induced emission effect (AIE), indicating that the synthesized product is a class of compounds with AIE effect. Molecules with AIE effect have been widely used in optoelectronic materials and biomedicine, indicating that the material system also has potential applications in the above fields.

[0230] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing an alkenyl thioester compound, characterized in that: The following steps are involved: (1) mixing the thioacid and the 1,1-diaryl olefin compound uniformly, and reacting them at 30-150° C. for 6-12 hours under light conditions; (2) After the reaction in step (1) is completed, the reaction product is sequentially extracted, dried, distilled, and separated and purified to obtain an alkenyl thioester compound; The synthetic route is as follows:

2. The method for preparing an alkenyl thioester compound according to claim 4, characterized in that: The molar ratio of the thioacid and the 1,1-diaryl olefin compound in step (1) is 1:

1.

3. The method for preparing an alkenyl thioester compound according to claim 4, characterized in that: The thioacid in step (1) is a thioacid substituted with an alkyl, aryl or heteroaryl group.

4. The method for preparing an alkenyl thioester compound according to claim 4, characterized in that: The 1,1-diaryl olefin compound in step (1) is a 1,1-disubstituted aryl olefin.

5. The method for preparing an alkenyl thioester compound according to claim 4, characterized in that: The illumination in step (1) is any one of sunlight, ambient light, household energy-saving lamp, blue LED, white LED and green LED.

6. The method for preparing an alkenyl thioester compound according to claim 4, characterized in that: The extraction in step (2) is carried out using dichloromethane or ethyl acetate; The separation and purification adopts silica gel column chromatography.

7. An alkenyl thioester compound, characterized in that: The general structural formula of the compound is: Wherein, R is any one of an alkyl group, an aryl group and a heteroaryl group; R 1 is hydrogen or methyl; R 2 It is monosubstituted at the 2, 3, 4 positions, or disubstituted at the 2, 4 or 3, 4 positions, and the substituted group is any one of an electron withdrawing group, an electron donating group, a phenyl group, and a naphthyl group.

8. An alkenyl thioester compound according to claim 1, characterized in that: The alkyl group is any one of phenethyl, benzyl and cycloalkyl, the aryl group is any one of phenyl and substituted phenyl, and the heteroaryl group is any one of furyl and thienyl.

9. An alkenyl thioester compound according to claim 1, characterized in that: The compound is any one of the following structures:

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