Synthesis method of beta-carbonyl thioether compound

Abstract

The invention belongs to the technical field of synthetic chemistry, and particularly relates to a synthetic method of a beta-carbonyl thioether compound. According to the invention, alpha-bromostyrene is taken as an initial raw material, aryl (alkyl) thiotrimethylsilane or aryl (alkyl) thiophenol / alcohol is taken as a sulfur source, simultaneous construction of a C = O bond and a C-S bond is realized from olefin under the conditions of no catalyst and no additive, and a series of beta-carbonyl thioether compounds are synthesized with high yield. The synthesis method disclosed by the invention has the characteristics of mild reaction conditions, high reaction speed, simplicity and convenience in operation, high yield, strong substrate applicability, no need of a catalyst and an additive, no need of taking a carbonyl-containing compound as a raw material and the like. The beta-carbonyl thioether compound disclosed by the invention is widely applied to the aspects of natural products, organic synthesis, medicines, foods and the like. The synthesis method disclosed by the invention provides a widely applicable preparation method for the compound.

Description

Technical Field

[0001] The present invention belongs to the technical field of synthetic chemistry, and specifically relates to a method for synthesizing β-carbonyl sulfide compounds, which is widely used in the synthesis research of organic compounds, natural products, drugs, etc. containing β-carbonyl sulfide structures. Background Art

[0002] Sulfur is an essential element for life and is widely present in the human body, such as disulfide bonds between iron-sulfur proteins and polypeptides, as well as sulfur-containing amino acids such as cysteine ​​and methionine. Sulfur plays an important role in organic synthetic chemistry and medicinal chemistry, and many sulfur-containing compounds have important biological activities, such as anti-inflammatory, antibacterial, anti-tumor, anti-parasitic, and antiviral activities. The different oxidation states and bonding modes of sulfur atoms form a wide variety of sulfur-containing organic compounds, such as thioethers, sulfoxides, sulfones, sulfonates, and sulfonamides. These structures appear in many marketed drugs and are their core pharmacophores. Among FDA-approved drugs, sulfur is the most commonly occurring element besides carbon, hydrogen, nitrogen, and oxygen.

[0003] β-Carboxyl sulfide is a class of organic compounds with important applications in natural products, organic synthesis, medicine, food, and other fields. There have been many reports on its synthesis, which is mainly synthesized by metal catalysis, non-metallic promotion, and electrochemical methods. In transition metal-catalyzed reactions, the metal first combines with the substrate to form an enolate anion or coordinates to form a complex, and then participates in subsequent reactions. Yun-Hua He et al. developed an iron-mediated SS bond cleavage method. Under N2 conditions, an intermediate containing an iron-sulfur bond is generated. The intermediate then reacts with an α-carbonyl bromide compound to cleave the C-Br bond to generate the target compound (Synth. Commun., 2015, 45(15):1817-1822.). Bolm et al. used copper acetate as a catalyst and acetonitrile as a solvent. The reaction was carried out at 130°C in the presence of oxygen for 24 hours and obtained the target compound with a yield of 90% (Adv. Synth. Catal., 2013, 355(13):2558-2563.). In 2020, Ningbo Li's research group designed a β-oxygen-bridged binuclear Lewis acid titanium (salophen) perfluorooctane sulfonate complex [{Ti(salophen)H2O}2O][OSO2C4F9]2 as a catalyst. Under the action of zinc powder, β-carbonyl sulfide can be generated in excellent yield after only 1 hour of reaction at room temperature (Tetrahedron, 2020, 76(4):130750-130759.).

[0004]

[0005] In non-metal-promoted reactions, strong bases are often used as catalysts or additives to promote the reaction by activating the sulfur-containing substrate. In 2012, the Barrett group used KOH as a catalyst (ChemMedChem, 2012, 7(11):1909-1914.), in 2017, the Yang Zhou group used KI as a catalyst and K2S2O8 as an oxidant (Synlett, 2017, 28(17):2325-2329.), in 2018, the Grayson group added LDA as a catalyst (Tetrahedron, 2018, 74(5):556-563.), and in 2021, Lyu et al. used DBU as a catalyst (J.Am.Chem.Soc., 2021, 143(3):1341-1347.) to successfully synthesize β-carbonyl sulfide. In addition, the ionic liquid [BmIm]OH can catalyze the reaction of thiols with epoxides to form β-carbonyl sulfides (Aust. J. Chem., 2007, 60(4): 278-283.).

[0006]

[0007] Literature reports indicate that the synthesis of β-carbonyl sulfides, regardless of the method used, must begin with a carbonyl-containing substrate (e.g., bromophenone, a highly irritant) or its analogs, such as epoxides and 1,3-dicarbonyl compounds, in combination with various sulfur sources (e.g., thiols and disulfides) through transition metal catalysis and base promotion. The substrate for this type of reaction must contain a carbonyl group, and the reaction involves only the formation of a C-S bond.

[0008] Therefore, β-carbonyl sulfide compounds have the limitation that they must be prepared from carbonyl-containing substrates. It is necessary to develop a new synthetic route for β-carbonyl sulfide compounds to overcome the raw material limitation. Summary of the Invention

[0009] The present invention addresses the limitation problem in the literature that β-carbonyl sulfide compounds need to be prepared from carbonyl substrates, and develops an efficient synthesis method with green and mild reaction conditions and no need for catalysts or additives.

[0010] The technical solution adopted in the present invention is as follows:

[0011] The present invention provides a method for synthesizing a β-carbonyl sulfide compound. The method comprises the following steps: mixing a raw material olefin halide and a sulfur source, and adding an organic solvent to obtain a β-carbonyl sulfide compound;

[0012] The reaction equation of the synthesis method is shown in Formula I:

[0013]

[0014] In Formula I, the raw material olefin halide is selected from α-halogenated olefins; the R group of the α-halogenated olefin is selected from benzene and benzene substituents, naphthalene, and 1-12 C alkyl groups; the substituents in the benzene substituents of the R group include halogen, 1-12 C alkyl groups, and 1-12 C alkoxy groups, the number of substituents is 1-3, and the substitution position is any position on the benzene ring; X is a halogen atom;

[0015] In formula I, the raw sulfur source is selected from arylthiotrimethylsilane, aralkylthiotrimethylsilane, thiophenol or thiol;

[0016] The R' group is selected from benzene and benzene substituents, thiophene, and 3-12 C alicyclic hydrocarbons; the substituents in the benzene substituents of the R' group include halogen, 1-12 C alkyl, and 1-12 C alkoxy, the number of substituents is 1-3, and the substitution position is any position on the benzene ring;

[0017] The R" group is selected from H and trimethylsilyl.

[0018] Preferably, the α-halogenated olefin includes one of α-bromostyrene, α-bromo-o-methylstyrene, α-bromo-m-methylstyrene, α-bromo-p-methylstyrene, α-bromo-p-methoxystyrene, α-bromo-p-tert-butylstyrene, α-bromo-p-fluorostyrene, α-bromo-2-naphthylethylene, and 2-bromo-1-butene.

[0019] Preferably, the sulfur source includes one of o-methylthiophenol, p-methylthiophenol, o-isopropylthiophenol, p-tert-butylthiophenol, p-methoxythiophenol, p-fluorothiophenol, p-chlorothiophenol, 3,4-dimethoxythiophenol, 2-thiophenethiophenol, 1-adamantanethiol, and phenylthiotrimethylsilane.

[0020] Preferably, the molar ratio of the α-haloolefin, aryl(alkyl)thiotrimethylsilane or aryl(alkyl)thiophenol / alcohol is 1:1.5-2.5.

[0021] Preferably, the reaction temperature is room temperature.

[0022] Preferably, the reaction time is 1 to 12 hours.

[0023] Preferably, the organic solvent for the reaction is N,N-dimethylformamide.

[0024] Preferably, the reaction is carried out under air atmosphere.

[0025] Preferably, the β-carbonyl sulfide compound specifically includes the following compounds:

[0026]

[0027] The present invention has the following advantages: α-haloolefins are used as substrates, aryl(alkyl)thiotrimethylsilane or aryl(alkyl)thiophenol / alcohol as a sulfur source, and oxygen in air is used as an oxidant at room temperature to synthesize a series of β-carbonyl sulfide compounds in high yields. Compared with the existing technology, the synthesis method of the present invention has the following advantages:

[0028] (1) The present invention uses α-haloolefins as substrates, breaking through the limitation that carbonyl-containing substrates must be used to prepare β-carbonyl sulfide compounds;

[0029] (2) The present invention simultaneously constructs two chemical bonds, C=O and CS;

[0030] (3) The method of the present invention does not require any catalyst or additive, is green and efficient, and operates under mild conditions;

[0031] (4) The synthesis method of the present invention has a simple reaction system and is easy to operate;

[0032] (5) The synthetic method of the present invention has high yield and a wide range of substrate applications.

[0033] The β-carbonyl sulfide compounds efficiently synthesized by the present invention are important skeletons of many drugs and bioactive molecules. The synthesis method of the present invention provides a widely applicable preparation method for the synthesis of such compounds. DETAILED DESCRIPTION

[0034] Example 1

[0035] Synthesis (3a) from α-bromostyrene (1a) and o-methylthiophenol (2a):

[0036]

[0037] α-Bromostyrene (1a) (0.6 mmol), o-methylthiophenol (2a) (1.5 mmol), and DMF (6 mL) were added to a 10 mL reaction tube and reacted at room temperature under air until the substrate completely disappeared (TLC monitoring, 1 h). The mixture was extracted three times with ethyl acetate and saturated aqueous sodium carbonate. The organic phases were combined, dried, and separated by column chromatography to obtain light yellow crystals in an 80% yield.

[0038] 1 H NMR (300MHz, CDCl3) δ8.00–7.92(m,2H),7.62–7.54(m,1H),7.46(tt,J=6.8, 1.4Hz,2H),7.39–7.32(m,1H),7.21–7.10(m,3H),4.25(s,2H),2.39(s,3H). 13C NMR (75MHz, CDCl3) δ194.02,138.62,135.32,133.94,133.43,130.27,130.14,128.63,128.62,126.99,126.62,40.44,20.43.

[0039] Example 2

[0040] Synthesis (3b) from α-bromostyrene (1a) and p-methylthiophenol (2b):

[0041]

[0042] α-Bromostyrene (1a) (0.6 mmol), p-methylthiophenol (2b) (1.5 mmol), and DMF (6 mL) were added to a 10 mL reaction tube and reacted at room temperature under air until the substrate completely disappeared (TLC monitoring, 1 h). Ethyl acetate and saturated aqueous sodium carbonate were added and extracted three times. The organic phases were combined, dried, and separated by column chromatography to obtain a light yellow oily liquid in an 86% yield.

[0043] 1 H NMR (300MHz, CDCl3) δ7.98–7.91(m,2H),7.61–7.53(m,1H),7.45(dd,J=8.3,6 .8Hz,2H),7.34–7.27(m,2H),7.10(d,J=8.0Hz,2H),4.22(s,2H),2.32(s,3H). 13 C NMR (75MHz, CDCl3) δ194.17,137.47,135.38,133.41,131.44,130.88,129.88,128.71,128.65,41.80,21.12.

[0044] Example 3

[0045] Synthesis of (3c) using α-bromostyrene (1a) and o-isopropylthiophenol (2c) as raw materials:

[0046]

[0047] α-Bromostyrene (1a) (0.6 mmol), o-methylthiophenol (2b) (1.5 mmol), and DMF (6 mL) were added to a 10 mL reaction tube and reacted at room temperature under air until the substrate disappeared completely (TLC monitoring, 2 h). Ethyl acetate and saturated aqueous sodium carbonate were added three times for extraction. The organic phases were combined, dried, and separated by column chromatography to obtain a light yellow oily liquid in a yield of 76%.

[0048] 1 H NMR (300MHz, CDCl3) δ7.97–7.88(m,2H),7.59–7.52(m,1H),7.47–7.36(m,3H),7.23(dd,J=6.1,1.7H z,2H),7.12(ddd,J=7.7,6.4,2.4Hz,1H),4.22(s,2H),3.47(p,J=6.9Hz,1H),1.16(d,J=6.9Hz,6H). 13 C NMR (75MHz, CDCl3) δ194.20, 149.66, 135.47, 133.49, 132.87, 131.51, 128.72 (d, J = 4.2Hz), 127.82, 126.55, 125.80, 41.75, 30.42, 23.59.

[0049] Example 4

[0050] Synthesis (3d) from α-bromostyrene (1a) and 4-tert-butylthiophenol (2d):

[0051]

[0052] α-Bromostyrene (1a) (0.6 mmol), p-methylthiophenol (2a) (1.5 mmol), and DMF (6 mL) were added to a 10 mL reaction tube and reacted at room temperature under air until the substrate completely disappeared (TLC monitoring, 2 h). Ethyl acetate and saturated aqueous sodium carbonate were added and extracted three times. The organic phases were combined, dried, and separated by column chromatography to obtain a light yellow oily liquid in an 88% yield.

[0053] 1 H NMR (300MHz, CDCl3) δ7.98–7.91(m,2H),7.60–7.53(m,1H),7.48–7.41(m,2H),7.38–7.29(m,4H),4.26(s,2H),1.31(s,9H). 13 C NMR (75MHz, CDCl3) δ194.26,150.46,135.44,133.41,131.16,130.82,128.70,128.65,126.15,41.62,34.53,31.26.

[0054] Example 5

[0055] Synthesis (3e) from α-bromostyrene (1a) and p-methoxythiophenol (2e):

[0056]

[0057] α-Bromostyrene (1a) (0.6 mmol), p-methoxythiophenol (2e) (1.5 mmol), and DMF (6 mL) were added to a 10 mL reaction tube and reacted at room temperature under air until the substrate disappeared completely (TLC monitoring, 4 h). Ethyl acetate and saturated aqueous sodium carbonate were added and extracted three times. The organic phases were combined, dried, and separated by column chromatography to obtain a light yellow oily liquid in an 81% yield.

[0058] 1 H NMR (300MHz, CDCl3) δ7.96–7.85(m,2H),7.60–7.50(m,1H),7.43(dd,J=8.3, 6.8Hz,2H),7.39–7.28(m,2H),6.85–6.77(m,2H),4.12(s,2H),3.75(s,3H). 13 C NMR (75MHz, CDCl3) δ194.29,159.67,135.39,134.58,133.32,128.69,128.61,124.51,114.68,55.27,42.76.

[0059] Example 6

[0060] Synthesis of (3f) using α-bromostyrene (1a) and p-fluorothiophenol (2f) as raw materials:

[0061]

[0062] α-Bromostyrene (1a) (0.6 mmol), p-fluorothiophenol (2f) (1.5 mmol), and DMF (6 mL) were added to a 10 mL reaction tube and reacted at room temperature under air until the substrate disappeared completely (TLC monitoring, 4 h). Ethyl acetate and saturated aqueous sodium carbonate were added three times for extraction. The organic phases were combined, dried, and separated by column chromatography to obtain a light yellow oily liquid in an 85% yield.

[0063] 1 H NMR (300MHz, CDCl3) δ8.00–7.84(m,2H),7.62–7.52(m,1H),7.50–7.31(m,4H),7.06–6.86(m,2H),4.20(s,2H). 13C NMR(75MHz, CDCl3)δ193.96,162.40(d,J=247.7Hz),135.26,133.90,133.79,1 33.55, 129.46 (d, J = 3.4Hz), 128.70 (d, J = 3.4Hz), 116.22 (d, J = 22.0Hz), 42.07.

[0064] Example 7

[0065] Synthesized from α-bromostyrene (1a) and p-chlorothiophenol (2g) (3g):

[0066]

[0067] α-Bromostyrene (1a) (0.6 mmol), p-chlorothiophenol (2 g) (1.5 mmol), and DMF (6 mL) were added to a 10 mL reaction tube and reacted at room temperature under air until the substrate disappeared completely (TLC monitoring, 4 h). Ethyl acetate and saturated aqueous sodium carbonate were added and extracted three times. The organic phases were combined, dried, and separated by column chromatography to obtain a light yellow oily liquid in an 83% yield.

[0068] 1 H NMR (300MHz, CDCl3) δ7.96–7.86(m,2H),7.61–7.51(m,1H),7.48–7.38(m,2H),7.33–7.25(m,2H),7.24–7.15(m,2H),4.23(s,2H). 13 C NMR (75MHz, CDCl3) δ193.74,135.18,133.65,133.24,133.18,131.84,129.20,128.77,128.67,41.19 .

[0069] Example 8

[0070] Synthesis (3h) using α-bromostyrene (1a) and 3,4-dimethoxythiophenol (2h) as raw materials:

[0071]

[0072] α-Bromostyrene (1a) (0.6 mmol), p-methoxythiophenol (2h) (1.5 mmol), and DMF (6 mL) were added to a 10 mL reaction tube and reacted at room temperature under air until the substrate disappeared completely (TLC monitoring, 12 h). Ethyl acetate and saturated aqueous sodium carbonate were added and extracted three times. The organic phases were combined, dried, and separated by column chromatography to obtain a light yellow oily liquid in a 65% yield.

[0073] 1 H NMR (300MHz, CDCl3) δ7.88(dt,J=7.2,1.4Hz,2H),7.56–7.49(m,1H),7.41(dd,J=8.2,6.8Hz,2H),6.97(d d,J=8.3,2.1Hz,1H),6.89(d,J=2.1Hz,1H),6.73(d,J=8.3Hz,1H),4.13(s,2H),3.81(s,3H),3.77(s,3H). 13 C NMR (75MHz, CDCl3) δ194.39,149.14,148.89,135.38,133.33,128.67,128.58,125.63,124.87,115.85,111.46,55.83,42.59.

[0074] Example 9

[0075] Synthesis of (3i) using α-bromostyrene (1a) and 2-thiophenethiophenol (2i) as raw materials:

[0076]

[0077] α-Bromostyrene (1a) (0.6 mmol), 2-thiophenethiophenol (2i) (1.5 mmol), and DMF (6 mL) were added to a 10 mL reaction tube and reacted at room temperature under air until the substrate disappeared completely (TLC monitoring, 12 h). Ethyl acetate and saturated aqueous sodium carbonate were added three times for extraction. The organic phases were combined, dried, and separated by column chromatography to obtain a purple oily liquid in a 69% yield.

[0078] 1 H NMR (300MHz, CDCl3) δ7.94–7.87(m,2H),7.61–7.55(m,1H),7.49–7.43(m,2H),7.37(dd, J=5.4,1.3Hz,1H),7.12(dd,J=3.6,1.3Hz,1H),6.95(dd,J=5.4,3.6Hz,1H),4.17(s,2H). 13 C NMR (75MHz, CDCl3) δ194.00,135.46,135.44,133.59,132.21,130.73,128.78,128.75,127.80,45.36.

[0079] Example 10

[0080] Synthesis (3j) from α-bromostyrene (1a) and 1-adamantanethiol (2j):

[0081]

[0082] α-Bromostyrene (1a) (0.6 mmol), 1-adamantanethiol (2j) (1.2 mmol), and DMF (6 mL) were added to a 10 mL reaction tube and reacted at room temperature under air until the substrate disappeared completely (TLC monitoring, 12 h). Ethyl acetate and saturated aqueous sodium carbonate were added and extracted three times. The organic phases were combined, dried, and separated by column chromatography to obtain a light yellow oily liquid in a 34% yield.

[0083] 1 H NMR (300MHz, CDCl3) δ7.99–7.93(m,2H),7.59–7.52(m,1H),7.46(dd,J=8.3,6 .7Hz,2H),3.86(s,2H),2.07–2.01(m,3H),1.88(d,J=3.0Hz,6H),1.67(s,6H). 13 C NMR (75MHz, CDCl3) δ196.68,135.69,133.35,128.89,128.68,46.00,43.30,36.22,33.18,29.79.

[0084] Example 11

[0085] Synthesis (3k) using α-bromo-o-methylstyrene (1b) and p-methylthiophenol (2a) as raw materials:

[0086]

[0087] α-Bromo-o-methylstyrene (1b) (0.6 mmol), p-methylthiophenol (2a) (1.5 mmol), and DMF (6 mL) were added to a 10 mL reaction tube and reacted at room temperature under air until the substrate disappeared completely (TLC monitoring, 2 h). Ethyl acetate and saturated aqueous sodium carbonate were added three times for extraction. The organic phases were combined, dried, and separated by column chromatography to obtain a light yellow oily liquid in a yield of 78%.

[0088] 1 H NMR (300MHz, CDCl3) δ7.65 (dd, J=8.2, 1.4Hz, 1H), 7.43 (td, J=7.7, 7.3, 1.4Hz, 1H) ,7.36–7.25(m,4H),7.14(d,J=8.0Hz,2H),4.24(s,2H),2.48(s,3H),2.37(s,3H). 13C NMR (75MHz, CDCl3) δ197.78,139.13,137.21,136.12,132.06,131.68,131.06,130.99,129.81,128.80,125.58,44.08,21.25,21.09.

[0089] Example 12

[0090] Synthesis (3l) using α-bromo-m-methylstyrene (1c) and p-methylthiophenol (2a) as raw materials:

[0091]

[0092] α-Bromo-m-methylstyrene (1c) (0.6 mmol), p-methylthiophenol (2a) (1.5 mmol), and DMF (6 mL) were added to a 10 mL reaction tube and reacted at room temperature under air until the substrate disappeared completely (TLC monitoring, 2 h). The mixture was extracted three times with ethyl acetate and saturated aqueous sodium carbonate. The organic phases were combined, dried, and separated by column chromatography to obtain white crystals in a yield of 77%.

[0093] 1 H NMR (300MHz, CDCl3) δ7.74(dd,J=6.0,1.9Hz,2H),7.41–7.28(m,4H),7.13–7.06(m,2H),4.21(s,2H),2.39(s,3H),2.32(s,3H). 13 C NMR (75MHz, CDCl3) δ194.36,138.44,137.41,135.42,134.19,131.44,131.02,129.85,129.20,128.51,125.92,41.88,21.34,21.10.

[0094] Example 13

[0095] Synthesis (3m) from α-bromo-4-methylstyrene (1d) and 4-methylthiophenol (2a):

[0096]

[0097] α-Bromo-4-methylstyrene (1d) (0.6 mmol), p-methylthiophenol (2a) (0.9 mmol), and DMF (6 mL) were added to a 10 mL reaction tube and reacted at room temperature under air until the substrate disappeared completely (TLC monitoring, 2 h). Ethyl acetate and saturated aqueous sodium carbonate were added three times for extraction. The organic phases were combined, dried, and separated by column chromatography to obtain a light yellow oily liquid in an 89% yield.

[0098] 1 H NMR (300MHz, CDCl3) δ7.86–7.76(m,2H),7.30–7.19(m,4H),7.06(d,J=8.0Hz,2H),4.16(s,2H),2.38(s,3H),2.28(s,3H). 13 C NMR (75MHz, CDCl3) δ193.81,144.26,137.29,132.86,131.25,131.06,129.82,129.32,128.80,41.70,21.69,21.08.

[0099] Example 14

[0100] Synthesis (3n) using α-bromo-4-methoxystyrene (1e) and 4-methylthiophenol (2a) as raw materials:

[0101]

[0102] α-Bromo-4-methoxystyrene (1e) (0.6 mmol), p-methylthiophenol (2a) (1.5 mmol), and DMF (6 mL) were added to a 10 mL reaction tube and reacted at room temperature under air until the substrate disappeared completely (TLC monitoring, 2 h). Ethyl acetate and saturated aqueous sodium carbonate were added three times for extraction. The organic phases were combined, dried, and separated by column chromatography to obtain a light yellow oily liquid in an 83% yield.

[0103] 1 H NMR (300MHz, CDCl3) δ7.94–7.88(m,2H),7.34–7.26(m,2H),7.13–7.03(m,2H),6.94–6.89(m,2H),4.17(s,2H),3.85(s,3H),2.30(s,3H). 13 C NMR (75MHz, CDCl3) δ192.85,163.70,137.29,131.22,131.16,131.04,129.84,128.36,113.81,55.51,41.56,21.10.

[0104] Example 15

[0105] Synthesis (3o) from α-bromo-4-tert-butylstyrene (1f) and 4-methylthiophenol (2a):

[0106]

[0107] α-Bromo-4-tert-butylstyrene (1f) (0.6 mmol), p-methylthiophenol (2a) (1.5 mmol), and DMF (6 mL) were added to a 10 mL reaction tube and reacted at room temperature under air until the substrate disappeared completely (TLC monitoring, 4 h). Ethyl acetate and saturated aqueous sodium carbonate were added three times for extraction. The organic phases were combined, dried, and separated by column chromatography to obtain a light yellow oily liquid in a 67% yield.

[0108] 1 H NMR (300MHz, CDCl3) δ7.95–7.87(m,2H),7.52–7.44(m,2H),7.36–7.28(m,2H),7.14–7.06(m,2H),4.22(s,2H),2.32(s,3H),1.36(s,9H). 13 C NMR (75MHz, CDCl3) δ193.76,157.13,137.29,132.81,131.28,131.11,129.84,128.69,125.61,41.69,35.15,31.08,21.12.

[0109] Example 16

[0110] Synthesized from α-bromo-4-fluorostyrene (1g) and 4-methylthiophenol (2a) (3p):

[0111]

[0112] α-Bromo-4-fluorostyrene (1 g) (0.6 mmol), p-methylthiophenol (2a) (1.5 mmol), and DMF (6 mL) were added to a 10 mL reaction tube and reacted at room temperature under air until the substrate completely disappeared (TLC monitoring, 4 h). The mixture was extracted three times with ethyl acetate and saturated aqueous sodium carbonate. The organic phases were combined, dried, and separated by column chromatography to obtain white crystals in a yield of 76%.

[0113] 1 H NMR (300MHz, CDCl3) δ7.99–7.88(m,2H),7.31–7.24(m,2H),7.09(td,J=8.4,2.0Hz,4H),4.15(s,2H),2.29(s,3H). 13C NMR (75MHz, CDCl3) δ192.69, 165.83 (d, J = 255.4Hz), 137.67, 131.78 (d, J = 3.0Hz), 131.54(d,J=4.1Hz),131.38,130.61,129.93,115.77(d,J=22.0Hz),41.66,21.11.

[0114] Example 17

[0115] Synthesis (3q) from α-bromo-2-naphthylethylene (1h) and phenylthiotrimethylsilane (2k):

[0116]

[0117] α-Bromo-2-naphthylethylene (1h) (0.6 mmol), phenylthiotrimethylsilane (2k) (1.5 mmol), and DMF (6 mL) were added to a 10 mL reaction tube and reacted at room temperature under air until the substrate completely disappeared (TLC monitoring, 5 h). Ethyl acetate and saturated aqueous sodium carbonate were added and extracted three times. The organic phases were combined, dried, and separated by column chromatography to obtain a light yellow oily liquid in an 80% yield.

[0118] 1 H NMR (300MHz, CDCl3) δ8.39–8.32(m,1H),7.95(dd,J=8.6,1.8Hz,1H),7.82(td,J=8.9, 8.0,5.6Hz,3H),7.57–7.46(m,2H),7.42–7.34(m,2H),7.27–7.14(m,3H),4.33(s,2H). 13 CNMR (75MHz, CDCl3) δ194.00,135.63,134.87,132.60,132.33,130.56,130. 50,129.62,129.09,128.73,128.54,127.76,127.10,126.86,124.14,41.28.

[0119] Example 18

[0120] Synthesis of (3r) using 2-bromo-1-butene (1i) and phenylthiotrimethylsilane (2k) as raw materials:

[0121]

[0122] 2-Bromo-1-butene (1i) (0.6 mmol), phenylthiotrimethylsilane (2k) (1.2 mmol), and DMF (6 mL) were added to a 10 mL reaction tube and reacted at room temperature under air until the substrate completely disappeared (TLC monitoring, 6 h). Ethyl acetate and saturated aqueous sodium carbonate were added and extracted three times. The organic phases were combined, dried, and separated by column chromatography to obtain a light yellow oily liquid in a 34% yield.

[0123] 1 H NMR (300MHz, CDCl3) δ7.35–7.26(m,4H),7.25–7.16(m,1H),3.68(s,2H),2.62(q,J=7.3Hz,2H),1.05(t,J=7.3Hz,3H). 13 C NMR (75MHz, CDCl3) δ206.44,135.00,129.57,129.25,126.92,43.72,34.04,7.99.

Claims

1. A method for synthesizing a β-carbonyl sulfide compound, characterized in that: The synthesis method comprises the following steps: mixing a raw material olefin halide and a sulfur source, adding an organic solvent, and reacting to obtain a β-carbonyl sulfide compound; The raw material olefin halide is selected from α-haloolefins; The raw sulfur source is selected from arylthiotrimethylsilane, aralkylthiotrimethylsilane, thiophenol or thiol.

2. The method for synthesizing β-carbonyl sulfide compounds according to claim 1, characterized in that: The α-halogenated olefin includes one of α-bromostyrene, α-bromo-o-methylstyrene, α-bromo-m-methylstyrene, α-bromo-p-methylstyrene, α-bromo-p-methoxystyrene, α-bromo-p-tert-butylstyrene, α-bromo-p-fluorostyrene, α-bromo-2-naphthylethylene, and 2-bromo-1-butene.

3. The method for synthesizing β-carbonyl sulfide compounds according to claim 1, characterized in that: The sulfur source includes one of o-methylthiophenol, p-methylthiophenol, o-isopropylthiophenol, p-tert-butylthiophenol, p-methoxythiophenol, p-fluorothiophenol, p-chlorothiophenol, 3,4-dimethoxythiophenol, 2-thiophenethiophenol, 1-adamantanethiol, and phenylthiotrimethylsilane.

4. The method for synthesizing β-carbonyl sulfide compounds according to claim 1, characterized in that: The molar ratio of the α-halogenated olefin, aryl(alkyl)thiotrimethylsilane or aryl(alkyl)thiophenol to the alcohol is 1:1.5-2.

5.

5. The method for synthesizing β-carbonyl sulfide compounds according to claim 1, wherein The reaction temperature is room temperature.

6. The method for synthesizing β-carbonyl sulfide compounds according to claim 1, characterized in that: The reaction time is 1 to 12 hours.

7. The method for synthesizing β-carbonyl sulfide compounds according to claim 1, characterized in that: The organic solvent for the reaction is N,N-dimethylformamide.

8. The method for synthesizing β-carbonyl sulfide compounds according to claim 1, characterized in that: The reaction was carried out under air atmosphere.

9. The method for synthesizing β-carbonyl sulfide compounds according to any one of claims 1 to 8, characterized in that: The β-carbonyl sulfide compound specifically includes the following compounds:

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