A method for preparing sulfoxide compounds by catalytic oxidation of thioether

Abstract

The invention discloses a novel method for preparing sulfoxide compounds by catalytic oxidation of sulfide, wherein the method realizes the oxidation synthesis of sulfoxide compounds of kilograms of sulfide under very mild conditions with or without solvent by screening catalysts and solvents. The method of the invention is compatible with alkyl-alkyl, alkyl-aryl, aryl-aryl sulfides and sulfur-containing heterocyclic compounds. The preparation method of the invention has broad application prospects.

Description

Technical Field

[0001] The invention belongs to the technical field of organic compound process application and relates to a novel method for preparing sulfoxide compounds by catalytic oxidation of sulfide. Background Art

[0002] Sulfoxide compounds are widely found in pesticides and medicines, such as the insecticide fipronil and omeprazole and rabeprazole for treating gastrointestinal diseases. The global sales of omeprazole alone reached 17 billion US dollars in 2007. Bulk chemical products such as dimethyl sulfoxide (DMSO) can not only be used as a solvent, but also have applications in many fields, such as medicine and electronics. The global annual production is expected to be around 120,000 tons in 2020.

[0003] In addition, since the acidic gases or liquids produced by the combustion of sulfides can corrode machinery and pollute the atmosphere, sulfides such as mercaptans, sulfides, disulfides and heterocyclic sulfides present in fuel need to be desulfurized before entering the market. Converting these sulfides into sulfoxide compounds through oxidation and then removing them in a targeted manner is an effective desulfurization method.

[0004] Finally, waste oil is a renewable resource that can be recycled as high-quality fuel, but it also needs to be desulfurized before use. Converting residual sulfides into sulfoxide compounds and then removing them in a targeted manner is also an important approach.

[0005] Therefore, the development of a synthesis method for oxidizing sulfides to sulfoxides by inexpensive metal catalysis can not only significantly reduce the production cost of sulfoxides, but also achieve the desulfurization of fuel oil and waste oil at a low cost. It is of great significance and has always attracted the attention of material and organic chemists. There are many methods for oxidizing sulfides to sulfoxides. In terms of oxidants, there are more than 14 known methods reported, such as oxygen (O 2) 、Hydrogen peroxide (H 2 O 2 ), urea peroxide (UHP), sodium hypochlorite (NaOCl), tert-butyl peroxide (tBuOOH), diacetone peroxide (DDO), iodobenzene oxide (PhIO), iodobenzene acetate (PhI(OAc) 2 ), nitric acid (HNO 3 ), meta-chloroperbenzoic acid (mCPBA), ferric nitrate (Fe(NO 3 ) 3 ), potassium peroxymonosulfonate (oxone), sodium bromate (NaBrO 3 ), manganese dioxide (MnO 2 ) etc. From the perspective of industrial cost, O 2It is the cleanest oxidant at the lowest cost, so in recent years, O 2 Oxidation of sulfides into sulfoxides has gradually become a research focus, such as the use of nitrogen dioxide (NO 2 ), nitrogen tetroxide (N 2 O 4 ), 2,2,6,6-tetramethylpiperidinium oxide (TEMPO), ferric nitrate nonahydrate complexed with ferric bromide (Fe(NO 3 ) 3 .9H 2 O / FeBr 3 ), organic photocatalysts and metal photocatalysis. However, when these methods are scaled up industrially, one or two of the factors, such as high catalyst value, expensive solvents, or difficulty in scaling up equipment, often limit their industrial application. Therefore, it is necessary to develop a solvent-free O 2 The oxidation method is of great significance and has huge industrial prospects. Summary of the invention

[0006] In order to solve the deficiencies in the prior art, the present invention aims to provide a novel method for preparing sulfoxide compounds by catalytic oxidation of sulfide.

[0007] The present invention can realize the oxidation of sulfide by oxygen under very mild conditions without solvent by screening new catalysts and additives. The sulfide may include alkyl-alkyl, alkyl-aryl, aryl-aryl sulfide and heterocyclic sulfur-containing compounds.

[0008] The present invention provides a novel method for preparing sulfoxide compounds by catalytic oxidation of sulfide. The reaction equation is as follows:

[0009]

[0010] The specific steps are as follows:

[0011] Using sulfide as raw material, an oxidation reaction occurs with oxygen under the action of a catalyst and an additive to selectively obtain sulfoxide compounds.

[0012] In the present invention, the oxygen comes from air or pure oxygen, preferably pure oxygen.

[0013] In the present invention, the catalyst is Fe(NO 3 ) 3 、Al(NO 3 ) 3 、KNO 3 、NaNO 3 、Cu(NO 3 ) 2 、Ce(NO 3 )4 、Se(NO 3 ) 3 、In(NO 3 ) 3 , Bi(NO 3 ) 3 One or more of the nitrates such as Fe(NO 3 ) 3 , including Fe(NO 3 ) 3 hydrate.

[0014] In the present invention, the catalyst is Fe(NO 3 ) 3 、Al(NO 3 ) 3 、KNO 3 、NaNO 3 、Cu(NO 3 ) 2 、Ce(NO 3 ) 4 、Se(NO 3 ) 3 、In(NO 3 ) 3 , Bi(NO 3 ) 3 One or more of the nitrates; preferably, Al(NO 3 ) 3 , including Al(NO 3 ) 3 hydrate.

[0015] In the present invention, the catalyst is Fe(NO 3 ) 3 、Al(NO 3 ) 3 、KNO 3 、NaNO 3 、Cu(NO 3 ) 2 、Ce(NO 3 ) 4 、Se(NO 3 ) 3 、In(NO 3 ) 3 , Bi(NO 3 ) 3 Preferably, Cu(NO 3 ) 3 , including Cu(NO 3 ) 3 hydrate.

[0016] In the present invention, the catalyst is Fe(NO 3 ) 3 、Al(NO 3 ) 3 、KNO 3 、NaNO 3 、Cu(NO 3 ) 2 、Ce(NO 3 ) 4 、Se(NO 3 ) 3 、In(NO 3 ) 3 , Bi(NO 3 ) 3 One or more of the nitrates; preferably, Ce(NO 3 ) 4 , including Ce(NO 3 ) 4 hydrate.

[0017] In the present invention, the catalyst is Fe(NO 3 ) 3 、Al(NO 3 ) 3 、KNO 3 、NaNO 3 、Cu(NO 3 ) 2 、Ce(NO 3 ) 4 、Se(NO 3 ) 3 、In(NO 3 ) 3 , Bi(NO 3 ) 3 One or more of the nitrates; preferably, Se(NO 3 ) 3 , including Se(NO 3 ) 3 hydrate.

[0018] In the present invention, the catalyst is Fe(NO 3 ) 3 、Al(NO 3 ) 3 、KNO 3 、NaNO 3 、Cu(NO 3 ) 2 、Ce(NO 3 ) 4 、Se(NO 3 ) 3、In(NO 3 ) 3 , Bi(NO 3 ) 3 Preferably, Cu(NO 3 ) 3 , including Cu(NO 3 ) 3 hydrate.

[0019] In the present invention, the catalyst is Fe(NO 3 ) 3 、Al(NO 3 ) 3 、KNO 3 、NaNO 3 、Cu(NO 3 ) 2 、Ce(NO 3 ) 4 、Se(NO 3 ) 3 、In(NO 3 ) 3 , Bi(NO 3 ) 3 One or more of the nitrates; preferably, In(NO 3 ) 3 , including In(NO 3 ) 3 hydrate.

[0020] In the present invention, the catalyst is Fe(NO 3 ) 3 、Al(NO 3 ) 3 、KNO 3 、NaNO 3 、Cu(NO 3 ) 2 、Ce(NO 3 ) 4 、Se(NO 3 ) 3 、In(NO 3 ) 3 , Bi(NO 3 ) 3 One or more of the nitrates; preferably, Bi(NO 3 ) 3 , including Bi(NO 3 ) 3 hydrate.

[0021] In the present invention, the additive is one or more of trifluoroacetic acid, acetic acid, propionic acid, butyric acid, trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid; preferably, trifluoroacetic acid.

[0022] In the present invention, the additive is one or more of trifluoroacetic acid, acetic acid, propionic acid, butyric acid, trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid; preferably, it is acetic acid.

[0023] In the present invention, the additive is one or more of trifluoroacetic acid, acetic acid, propionic acid, butyric acid, trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid; preferably, it is propionic acid.

[0024] In the present invention, the additive is one or more of trifluoroacetic acid, acetic acid, propionic acid, butyric acid, trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid; preferably, it is butyric acid.

[0025] In the present invention, the additive is one or more of trifluoroacetic acid, acetic acid, propionic acid, butyric acid, trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid; preferably, it is trifluoromethanesulfonic acid.

[0026] In the present invention, the additive is one or more of trifluoroacetic acid, acetic acid, propionic acid, butyric acid, trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid; preferably, it is hydrochloric acid.

[0027] In the present invention, the additive is one or more of trifluoroacetic acid, acetic acid, propionic acid, butyric acid, trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid; preferably, it is sulfuric acid.

[0028] In the present invention, the additive is one or more of trifluoroacetic acid, acetic acid, propionic acid, butyric acid, trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid; preferably, methanesulfonic acid.

[0029] In the present invention, the additive is one or more of trifluoroacetic acid, acetic acid, propionic acid, butyric acid, trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid; preferably, it is p-toluenesulfonic acid.

[0030] In the present invention, the temperature of the oxidation reaction is room temperature (rt) - 120°C; preferably, room temperature 50°C.

[0031] In the present invention, the oxidation reaction time is 2-36 hours; preferably, it is 3 hours.

[0032] In the present invention, the molar amount of the catalyst is 5-10 mol% of the thioether; preferably, 10 mol%.

[0033] In the present invention, the molar amount of the additive is 3-20 equiv. of the thioether, preferably, 10.0 equiv.

[0034] Where R 1 , R 2 One or more selected from hydrogen, alkyl, and aryl, and its structural formula is shown in formula (1);

[0035]

[0036] Among them, R 1 Selected from hydrogen, alkyl, aryl and heterocycle, preferably, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, other alkyl, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-formylphenyl, 4-formylphenyl, other phenyl groups and thiophene, thiazole, benzothiophene, benzothiazole, benzisothiazole, dibenzothiophene, phenoxathiol, phenothiazine and thianthrene.

[0037] Among them, R 2 Selected from hydrogen, alkyl, aryl and heterocycle, preferably, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, other alkyl, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-formylphenyl, 4-formylphenyl, other phenyl groups and thiophene, thiazole, benzothiophene, benzothiazole, benzisothiazole, dibenzothiophene, phenoxathiol, phenothiazine and thianthrene.

[0038] The thioether, the structure of formula (1) includes but is not limited to the following parts:

[0039]

[0040]

[0041] The structural formula of the sulfoxide compound includes the following:

[0042]

[0043]

[0044] The beneficial effects of the present invention include: mild reaction conditions, simple reaction operation, use of oxygen as an oxidant, low catalyst price, no need to use a solvent, large-scale (kilogram level) preparation of sulfoxide compounds, reduced overall cost, and prospects for industrial application. DETAILED DESCRIPTION

[0045] The present invention is further described in detail with reference to the following specific examples. The process, conditions, experimental methods, etc. for implementing the present invention, except for the contents specifically mentioned below, are all common knowledge and common common sense in the art and are not particularly limited by the present invention.

[0046] The following examples of the present invention are about the preparation of sulfoxide compounds with reference to the following reaction formula:

[0047]

[0048] Example 1

[0049] Synthesis of compound 1:

[0050]

[0051] Dimethyl sulfide (124 g, 2.0 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (40.4 g, 0.1 mol, 5 mol%) and acetic acid (340 mL, 6.0 mol, 3.0 equiv.) were added to replace oxygen. The reaction was carried out at rt for 6 hours. The red color disappeared and the wall temperature returned to room temperature. The reaction was stopped and the solvent was dried by spin drying. The compound was filtered to obtain 1137.3 g (1.76 mmol, 88% yield) of a light yellow liquid.

[0052] The relevant characterization results of compound 1 are as follows:

[0053] 1 H NMR (400 MHz, CDCl 3 )δ2.63(s,6H). 13 C NMR (100 MHz, CDCl 3 )δ40.8.

[0054] Example 2

[0055] Synthesis of compound 2:

[0056]

[0057] Di-tert-butyl sulfide (1.5 g, 10.0 mmol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (404 mg, 1 mmol, 10 mol%) and acetic acid (6 mL, 100.0 mmol, 10 equiv.), replace oxygen, react at rt for 24 hours, stop the reaction, spin dry the solvent, wash with saturated sodium chloride aqueous solution, extract with ethyl acetate, and separate the organic phase by column chromatography to obtain 21.18 g (7.3 mmol, 73% yield) of colorless liquid compound.

[0058] The relevant characterization results of compound 2 are as follows:

[0059] 1 H NMR (400 MHz, CDCl 3 )δ2.70–2.53(m,4H),1.79–1.62(m,4H),1.55–1.32(m,4H),0.89–0.94(m,6H). 13 C NMR (100 MHz, CDCl 3 )δ52.0,24.5,22.0,13.5.

[0060] Example 3

[0061] Synthesis of compound 3:

[0062]

[0063] Dibenzyl sulfide (1.0 g, 5.0 mmol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (202 mg, 0.5 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 14 equiv.), replace oxygen, react at 50 ° C for 5 hours, stop the reaction, spin dry the solvent, wash with saturated sodium chloride aqueous solution, extract with ethyl acetate, and separate the organic phase by column chromatography to obtain 30.92 g (4.0 mmol, 79% yield) of a white solid compound.

[0064] The relevant characterization results of compound 3 are as follows:

[0065] 1 H NMR (500 MHz, CDCl 3 )δ7.35-7.40(m,10H),7.28-7.30(m,4H),3.90(q,J=13Hz,4H). 13 C NMR (125 MHz, CDCl 3 )δ130.1,128.9,128.3,57.3.

[0066] Example 4

[0067] Synthesis of compound 4:

[0068]

[0069] Thioanisole (1.2 g, 10.0 mmol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2O (404 mg, 1.0 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 7 equiv.), replace oxygen, react at 50 ° C for 2 hours, TLC detection of the reaction of the raw materials is complete, the solvent is spin-dried, washed with saturated sodium chloride aqueous solution, extracted with ethyl acetate, and separated by organic phase column chromatography to obtain 41.20 g (8.6 mmol, 86% yield) of a white solid compound.

[0070] The relevant characterization results of compound 4 are as follows:

[0071] 1 H NMR (500 MHz, CDCl 3 )δ7.59-7.61(m,2H),7.43-7.50(m,3H),2.68(s,3H). 13 CNMR (125MHz, CDCl 3 )δ145.4,130.9,129.2,123.3,43.7.

[0072] Example 5

[0073] Synthesis of compound 5:

[0074]

[0075] To a 25 mL reaction tube, phenethyl sulfide (1.0 g, 7.2 mmol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (291 mg, 0.72 mmol, 10 mol%) and acetic acid (4 mL, 72.0 mmol, 10 equiv.), replace oxygen, react at 50 ° C for 2 hours, TLC detection of the reaction of the raw materials is complete, the solvent is spin-dried, washed with saturated sodium chloride aqueous solution, extracted with ethyl acetate, and separated by organic phase column chromatography to obtain 51.02 g (6.6 mmol, 92% yield) of a white solid compound.

[0076] The relevant characterization results of compound 5 are as follows:

[0077] 1 H NMR (500 MHz, CDCl 3 )δ7.47-7.57(m,5H),2.73–2.86(m,2H),1.15(s,3H). 13 CNMR (125MHz, CDCl 3 )δ143.1,130.8,129.0,124.0,50.1,5.8.

[0078] Example 6

[0079] Synthesis of compound 6:

[0080]

[0081] 4-Chloroanisole (1.6 g, 10.0 mmol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (404 mg, 1.0 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 7 equiv.), replace oxygen, react at 50 ° C for 4 hours, TLC detection shows that the raw material has reacted completely, the solvent is spin-dried, washed with saturated sodium chloride aqueous solution, extracted with ethyl acetate, and separated by organic phase column chromatography to obtain 61.62 g (9.2 mmol, 92% yield) of a white solid compound.

[0082] The relevant characterization results of compound 6 are as follows:

[0083] 1 H NMR (500 MHz, CDCl 3 )δ7.50-7.60(m,4H),2.71(s,3H). 13 C NMR (125 MHz, CDCl 3 )δ144.2,137.2,129.6,124.9,44.1.

[0084] Example 7

[0085] Synthesis of compound 7:

[0086]

[0087] 4-Bromoanisyl thioether (1.0 g, 5.0 mmol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (202 mg, 0.5 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 14 equiv.), replace oxygen, react at 50 ° C for 2 hours, TLC detection of the reaction of the raw materials is complete, the solvent is spin-dried, washed with saturated sodium chloride aqueous solution, extracted with ethyl acetate, and separated by organic phase column chromatography to obtain 71.05 g (4.8 mmol, 95% yield) of a white solid compound.

[0088] The relevant characterization results of compound 7 are as follows:

[0089] 1 H NMR (400 MHz, CDCl 3)δ7.50-7.67(m,4H),2.69–2.71(m,3H). 13 C NMR (100 MHz, CDCl 3 )δ144.8,132.5,125.4,125.1,44.0.

[0090] Example 8

[0091] Synthesis of compound 8:

[0092]

[0093] 4-Iodoanisyl thioether (1.0 g, 4.0 mmol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (162 mg, 0.4 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 18 equiv.), replace oxygen, react at 50 ° C for 4 hours, TLC detection shows that the raw material has reacted completely, the solvent is spin-dried, washed with saturated sodium chloride aqueous solution, extracted with ethyl acetate, and separated by organic phase column chromatography to obtain 80.96 g (3.6 mmol, 90% yield) of a white solid compound.

[0094] The relevant characterization results of compound 8 are as follows:

[0095] 1 H NMR (400 MHz, CDCl 3 )δ7.83-7.87(m,2H),7.33-7.37(m,2H),2.66–2.72(m,3H). 13 C NMR (100 MHz, CDCl 3 )δ145.7,138.5,125.2,97.4,44.0.

[0096] Example 9

[0097] Synthesis of compound 9:

[0098]

[0099] 4-Formylbenzylthioether (1.5 g, 10.0 mmol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2O (404 mg, 1.0 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 7 equiv.), replace oxygen, react at 50 ° C for 6 hours, TLC detection shows that the raw material has reacted completely, the solvent is spin-dried, washed with saturated sodium chloride aqueous solution, extracted with ethyl acetate, and separated by organic phase column chromatography to obtain 91.31 g (7.9 mmol, 79% yield) of a white solid compound.

[0100] The relevant characterization results of compound 9 are as follows:

[0101] 1 H NMR (500 MHz, CDCl 3 )δ10.07(s,1H).8.03(d,J=8Hz,2H),7.80(d,J=8.5Hz,2H),2.76(s,3H). 13 C NMR (125 MHz, CDCl 3 )δ191.1,152.4,138.1,130.3,124.1,43.7.

[0102] Example 10

[0103] Synthesis of compound 10:

[0104]

[0105] 4-Formylanisole (1.0 g, 6.0 mmol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (242 mg, 0.6 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 12 equiv.), replace oxygen, react at 50 ° C for 6 hours, TLC detection shows that the raw material has reacted completely, the solvent is spin-dried, washed with saturated sodium chloride aqueous solution, extracted with ethyl acetate, and separated by organic phase column chromatography to obtain 100.76 g (4.2 mmol, 70% yield) of a white solid compound.

[0106] The relevant characterization results of compound 10 are as follows:

[0107] 1 H NMR (500 MHz, CDCl 3 )δ8.08(d,J=7.5Hz,2H),7.73(d,J=7.5Hz,2H),2.74(s,3H),2.62–2.63(m,3H). 13 C NMR (125 MHz, CDCl 3)δ197.0,150.9,139.0,129.1,123.7,43.8,26.7.

[0108] Embodiment 11

[0109] Synthesis of compound 11:

[0110]

[0111] 4-Cyanoisylthioether (1.0 g, 6.7 mmol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (283 mg, 0.7 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 10 equiv.), replace oxygen, react at 50 ° C for 5 hours, TLC detection shows that the raw material has reacted completely, the solvent is spin-dried, washed with saturated sodium chloride aqueous solution, extracted with ethyl acetate, and separated by organic phase column chromatography to obtain 0.98 g (5.9 mmol, 88% yield) of white solid compound 11.

[0112] The relevant characterization results of compound 11 are as follows:

[0113] 1 H NMR (300 MHz, CDCl 3 )δ7.74–7.84(m,4H),2.74–2.76(m,3H). 13 C NMR (75MHz, CDCl 3 )δ151.4,133.0,124.3,117.7,114.8,43.8.

[0114] Example 12

[0115] Synthesis of compound 12:

[0116]

[0117] Diphenyl sulfide (1.9 g, 10.0 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (404 mg, 1.0 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 7 equiv.), replace oxygen, react at 80 ° C for 9 hours, TLC detection of the reaction of the raw materials is complete, the solvent is spin-dried, washed with saturated sodium chloride aqueous solution, extracted with ethyl acetate, and separated by organic phase column chromatography to obtain a white solid compound 121.57 g (7.5 mmol, 75% yield).

[0118] The relevant characterization results of compound 12 are as follows:

[0119] 1 H NMR (500 MHz, CDCl 3 )δ7.63–7.64(m,4H),7.42–7.44(m,6H). 13 C NMR (125 MHz, CDCl 3 )δ145.5,130.9,129.2,124.7.

[0120] Embodiment 13

[0121] Synthesis of compound 13:

[0122]

[0123] Dibenzothiophene (1.9 g, 10.0 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (404 mg, 1.0 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 7 equiv.) were added to replace oxygen, and the reaction was carried out at 80°C for 36 hours. The reaction was stopped, the solvent was dried, and the mixture was washed with saturated sodium chloride aqueous solution. The mixture was extracted with ethyl acetate and separated by organic phase column chromatography to obtain 0.76 g (3.6 mmol, 36% yield) of white solid compound 13.

[0124] The relevant characterization results of compound 13 are as follows:

[0125] 1 H NMR (500 MHz, CDCl 3 )7.98(d,J=7.5Hz,2H),7.82(d,J=7.5Hz,2H),7.57–7.61(m,2H),7.49–7.53(m,2H). 13 C NMR (125 MHz, CDCl 3 )δ145.2,137.1,132.5,129.6,127.5,121.9.

[0126] Embodiment 14

[0127] Synthesis of compound 14:

[0128]

[0129] In a 25 mL reaction tube, thiophene (1.0 g, 5.0 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (202 mg, 0.5 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 14 equiv.), replace oxygen, react at 50 ° C for 2 hours, TLC detection shows that the raw material has reacted completely, the solvent is spin-dried, washed with saturated sodium chloride aqueous solution, extracted with ethyl acetate, and separated by organic phase column chromatography to obtain white solid compound 14 1.00 g (4.7 mmol, 93% yield).

[0130] The relevant characterization results of compound 14 are as follows:

[0131] 1 H NMR (400 MHz, CDCl 3 )δ7.93(dt,J=8.0,2.0Hz,2H),7.66–7.58(m,2H),7.47–7.34(m,4H). 13 C NMR (125 MHz, CDCl 3 )δ149.4,133.7,131.0,124.8,123.6,118.8.

[0132] Embodiment 15

[0133] Synthesis of compound 15:

[0134]

[0135] Thianthracene (1.1 g, 5.0 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (202 mg, 0.5 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 14 equiv.) were added to replace oxygen, and the reaction was carried out at 50°C for 1 hour. TLC detected that the reaction of the raw materials was complete. The solvent was spin-dried, the mixture was washed with saturated sodium chloride aqueous solution, extracted with ethyl acetate, and separated by organic phase column chromatography to obtain 1.10 g (4.8 mmol, 95% yield) of white solid compound 15.

[0136] The relevant characterization results of compound 15 are as follows:

[0137] 1 H NMR (500 MHz, CDCl 3)δ7.93(d,J=7.5Hz,2H),7.62(d,J=8.0Hz,2H),7.55(t,J=7.5Hz,2H),7.42(t,J=7.5Hz,2H). 13 C NMR (125 MHz, CDCl 3 )δ141.4,129.8,129.0,128.4,124.5.

[0138] Example 16

[0139] Synthesis of compound 16:

[0140]

[0141] Albendazole (1.1 g, 4.0 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (162 mg, 0.4 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 18 equiv.), replace oxygen, react at 80 ° C for 12 hours, TLC detection shows that the raw material has reacted completely, the solvent is spin-dried, washed with saturated sodium chloride aqueous solution, extracted with ethyl acetate, and separated by organic phase column chromatography to obtain 1.02 g (3.6 mmol, 89% yield) of white solid compound 16.

[0142] The relevant characterization results of compound 16 are as follows:

[0143] 1 H NMR (500 MHz, CDCl 3 )δ13.83(s,1H),10.77(s,1H),7.33–8.03(m,3H),4.03(s,3H),2.77–2.89(m,2H),1.63–1.85(m,2H),1.05(t,J=7.5Hz,3H). 13 C NMR (125 MHz, CDCl 3 )δ155.5,149.6,134.9,117.4,113.5,111.0,59.8,53.4,16.0,13.3.

[0144] Embodiment 17

[0145] Synthesis of compound 17:

[0146]

[0147] Triclabendazole (1.4 g, 4.0 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (162 mg, 0.4 mmol, 10 mol%) and trifluoroacetic acid (4 mL, 51.0 mmol, 11 equiv.), replace oxygen, react at room temperature for 3 hours, TLC detection shows that the raw material has reacted completely, the solvent is spin-dried, the mixture is washed with saturated sodium chloride aqueous solution, extracted with ethyl acetate, and separated by organic phase column chromatography to obtain 1.42 g (3.8 mmol, 95% yield) of white solid compound 17.

[0148] The relevant characterization results of compound 17 are as follows:

[0149] 1 H NMR (500 MHz, CDCl 3 )δ8.68(s,2H),7.58(s,1H),7.18(dd,J=8.0,1.0Hz,1H),7.14(s,1H),7.05(t,J=8.5Hz,1H),6.60(dd,J=8.0,1.0Hz,1H),2.74(s,3H). 13 C NMR (125 MHz, CDCl 3 )δ154.6,154.0,146.8,138.3,136.3,134.3,127.4,124.7,123.2,120.9,115.6,115.2,106.3,14.7.

[0150] Embodiment 18

[0151] Synthesis of compound 18:

[0152]

[0153] 4-Chloromethyl diphenyl sulfide (1.0 g, 4.3 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (162 mg, 0.43 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 17 equiv.), replace oxygen, react at room temperature for 3 hours, TLC detection shows that the raw material has reacted completely, the solvent is spin-dried, washed with saturated sodium chloride aqueous solution, extracted with ethyl acetate, and separated by organic phase column chromatography to obtain 180.91 g (3.7 mmol, 85% yield) of a viscous liquid compound.

[0154] The relevant characterization results of compound 18 are as follows:

[0155] 1 H NMR (500 MHz, CDCl 3 )δ7.69–7.61(m,4H),7.50–7.40(m,5H),4.56(s,2H). 13 CNMR (125MHz, CDCl 3 )δ145.8,145.3,140.4,131.2,129.4,125.1,124.7,45.2.

[0156] Embodiment 19

[0157] Synthesis of compound 19:

[0158]

[0159] 2-Methyldibenzothiophene (1.0 g, 4.8 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (192 mg, 0.48 mmol, 10 mol%) and trifluoroacetic acid (4 mL, 51.0 mmol, 11 equiv.), replace oxygen, react at room temperature for 3 hours, TLC detection shows that the raw material has reacted completely, the solvent is spin-dried, washed with saturated sodium chloride aqueous solution, extracted with ethyl acetate, and separated by organic phase column chromatography to obtain viscous liquid compound 19 0.77 g (3.6 mmol, 75% yield).

[0160] The relevant characterization results of compound 19 are as follows:

[0161] 1 H NMR (500 MHz, CDCl 3 )δ8.00(d,J=10.0Hz,1H),7.77(d,J=10.0Hz,1H),7.64–7.56(m,2H),7.50(dt,J=15.0,10.0Hz,2H),2.79(s,3H). 13 C NMR (126 MHz, CDCl 3 )δ144.2,142.6,138.8,136.8,132.4,132.0,130.6,129.0,126.9,121.6,119.1,18.3.

[0162] Embodiment 20

[0163] Synthesis of compound 20:

[0164]

[0165] N-methyldibenzothiazine (1.0 g, 4.7 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (188 mg, 0.47 mmol, 10 mol%) and acetic acid (4 mL, 70 mmol, 14 equiv.), replace oxygen, react at 50 ° C for 3 hours, TLC detection of the reaction of the raw materials was complete, the solvent was spin-dried, washed with saturated sodium chloride aqueous solution, extracted with ethyl acetate, and separated by organic phase column chromatography to obtain a viscous liquid compound 20 0.98 g (4.3 mmol, 91% yield).

[0166] The relevant characterization results of compound 20 are as follows:

[0167] 1 H NMR (500 MHz, CDCl 3 )δ7.94(dd,J=7.5,1.0Hz,2H),7.62(dd,J=14.5,7.0Hz,2H),7.39(d,J=8.5Hz,2H),7.26(dd,J=7.5,1.0Hz,2H),3.76(s,3H). 13 C NMR (125 MHz, CDCl 3 )δ139.9,132.7,131.0,124.6,121.8,115.5,35.3.

[0168] Embodiment 21

[0169] Synthesis of compound 21

[0170]

[0171] Fenbendazole (1.0 g, 3.3 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (132 mg, 0.33 mmol, 10 mol%) and trifluoroacetic acid (4 mL, 51.0 mmol, 14 equiv.) were added to replace oxygen and reacted at room temperature for 3 hours. TLC detected that the raw material had reacted completely. The solvent was spin-dried and the mixture was washed with saturated sodium chloride aqueous solution. The mixture was extracted with ethyl acetate and separated by organic phase column chromatography to obtain viscous liquid compound 21 1.0 g (3.2 mmol, 96% yield).

[0172] The relevant characterization results of compound 21 are as follows:

[0173] 1H NMR (500MHz, DMSO) δ7.71(d,J=5.0Hz,1H),7.65–7.60(m,2H),7.51–7.41(m,4H),7.35(dd,J=10.0,1.5Hz,1H),3.72(s,3H). 13 C NMR (125MHz, DMSO) δ156.1,154.11(s),147.5,137.6,129.9,129.2,123.9,120.7,117.6,38.8.

[0174] Embodiment 22

[0175] Synthesis of compound 22

[0176]

[0177] To a 25 mL reaction tube, perphenazine (1.0 g, 2.5 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (100 mg, 0.25 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 28 equiv.) were added to replace oxygen and reacted at 50 °C for 3 hours. TLC detected that the reaction of the raw material was complete. The solvent was spin-dried and the mixture was washed with saturated sodium chloride aqueous solution. The mixture was extracted with ethyl acetate and separated by organic phase column chromatography to obtain viscous liquid compound 22 0.89 g (2.1 mmol, 85% yield).

[0178] The relevant characterization results of compound 22 are as follows:

[0179] 1 H NMR (500 MHz, CDCl 3 )δ7.87(dd,J=7.5,1.0Hz,1H),7.79(d,J=8.0Hz,1H),7.58(dd,J=8.0,1.0Hz,1H),7.49(d,J=11.5Hz,2H),7.22(t,J=7.5Hz,1H),7. 15(dd,J=8.0,1.0Hz,1H),4.36–4.20(m,2H),3.58(t,J=5.0Hz,2H),3.00(s,1H),2.67–2.25(m,12H),2.00(dd,J=14.0,5.0Hz,2H).

[0180] 13 C NMR (125 MHz, CDCl 3)δ139.2,138.7,137.7,132.8,132.6,131.4,124.2,122.4,122.1,121.7,115.93,59.3,57.7,54.4,53.1,52.8,45.3,23.6.

[0181] Embodiment 23

[0182] Synthesis of compound 23

[0183]

[0184] 2-Chloroethylphenyl sulfide (1.7 g, 10.0 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (400 mg, 1.0 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 7 equiv.) were added to replace oxygen and reacted at 50 °C for 3 hours. TLC detected that the reaction of the raw materials was complete. The solvent was spin-dried and the mixture was washed with saturated sodium chloride aqueous solution. The mixture was extracted with ethyl acetate and separated by organic phase column chromatography to obtain viscous liquid compound 23 1.5 g (7.9 mmol, 79% yield).

[0185] The relevant characterization results of compound 23 are as follows:

[0186] 1 H NMR (500 MHz, CDCl 3 )δ7.64(dt,J=4.5,2.0Hz,2H),7.59–7.51(m,3H),4.01–3.93(m,1H),3.69–3.62(m,1H),3.21–3.13(m,2H). 13 C NMR (125 MHz, CDCl 3 )δ142.8,131.4,129.5,123.9,59.4,36.7.

[0187] Embodiment 24

[0188] Synthesis of compound 24

[0189]

[0190] 4-Methoxyanisole (1.0 g, 6.5 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2O (260 mg, 0.65 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 11 equiv.) were added to replace oxygen and reacted at room temperature for 3 hours. TLC detected that the raw material had reacted completely. The solvent was spin-dried and the mixture was washed with saturated sodium chloride aqueous solution. The mixture was extracted with ethyl acetate and separated by organic phase column chromatography to obtain viscous liquid compound 24 0.94 g (5.5 mmol, 85% yield).

[0191] The relevant characterization results of compound 24 are as follows:

[0192] 1 H NMR (400 MHz, CDCl 3 )δ7.61–7.51(m,2H),7.05–6.92(m,2H),3.87–3.78(m,3H),2.67(d,J=0.8Hz,3H). 13 C NMR (100 MHz, CDCl 3 )δ161.9,136.5,125.4,114.8,55.4,43.9.

[0193] Embodiment 25

[0194] Synthesis of compound 25

[0195]

[0196] 4-Nitroanisole (1.7 g, 10.0 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (400 mg, 1.0 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 7 equiv.) were added to replace oxygen and reacted at 50 °C for 3 hours. TLC detected that the reaction of the raw material was complete. The solvent was spin-dried and the mixture was washed with saturated sodium chloride aqueous solution. The mixture was extracted with ethyl acetate and separated by organic phase column chromatography to obtain viscous liquid compound 25 1.4 g (7.6 mmol, 76% yield).

[0197] The relevant characterization results of compound 25 are as follows:

[0198] 1 H NMR (400 MHz, CDCl 3 )δ8.36(d,J=8.8Hz,2H),7.82(d,J=8.8Hz,2H),2.77(s,3H). 13 C NMR (100 MHz, CDCl 3 )δ153.2,149.4,124.6,124.4,43.8.

[0199] Embodiment 26

[0200] Synthesis of compound 26

[0201]

[0202] Dioctyl sulfide (1.6 g, 6.2 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (248 mg, 0.62 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 11 equiv.) were added to replace oxygen and reacted at room temperature for 3 hours. TLC detected that the raw material had reacted completely. The solvent was spin-dried and the mixture was washed with saturated sodium chloride aqueous solution. The mixture was extracted with ethyl acetate and separated by organic phase column chromatography to obtain viscous liquid compound 26 1.4 g (5.8 mmol, 94% yield).

[0203] The relevant characterization results of compound 26 are as follows:

[0204] 1 H NMR (400 MHz, CDCl 3 )δ2.74–2.51(m,4H),1.74(m,4H),1.56–1.37(m,4H),1.28(m,16H),0.87(t,J=6.8Hz,6H). 13 C NMR (100 MHz, CDCl 3 )δ52.4,31.69,3.13,29.0,28.9,22.6,14.0.

[0205] Embodiment 27

[0206] Synthesis of compound 27

[0207]

[0208] 4-Methylphenylbenzene sulfide (1.0 g, 5.0 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (200 mg, 0.50 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 14 equiv.) were added to replace oxygen and reacted at 50 °C for 3 hours. TLC detected that the reaction of the raw materials was complete. The solvent was spin-dried and the mixture was washed with saturated sodium chloride aqueous solution. The mixture was extracted with ethyl acetate and separated by organic phase column chromatography to obtain viscous liquid compound 27 1.0 g (4.7 mmol, 93% yield).

[0209] The relevant characterization results of compound 27 are as follows:

[0210] 1 H NMR (400 MHz, CDCl 3 )δ7.66–7.59(m,2H),7.52(d,J=8.0Hz,2H),7.47–7.37(m,3H),7.24(t,J=6.4Hz,2H),2.34(s,3H). 13 C NMR (100 MHz, CDCl 3 )δ145.7,142.4,141.5,130.8,129.9,129.1,124.9,124.6,21.3.

[0211] Embodiment 28

[0212] Synthesis of compound 28

[0213]

[0214] Cyprodinil (1.4 g, 4.4 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (176 mg, 0.44 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 16 equiv.) were added to replace oxygen and reacted at room temperature for 3 hours. TLC detected that the reaction of the raw materials was complete. The solvent was spin-dried and the mixture was washed with saturated sodium chloride aqueous solution. The mixture was extracted with ethyl acetate and separated by organic phase column chromatography to obtain viscous liquid compound 28 1.3 g (3.9 mmol, 88% yield).

[0215] The relevant characterization results of compound 28 are as follows:

[0216] 1 H NMR (500 MHz, CDCl 3 )δ7.89(dd,J=7.5,1.5Hz,1H),7.81(d,J=8.0Hz,1H),7.66–7.57(m,1H),7.48(d,J=8.5Hz,2H),7.27(dd,J=9.5,5. 0Hz,1H),7.20(dd,J=8.0,1.5Hz,1H),4.43–4.28(m,2H),2.77(t,J=7.5Hz,2H),2.41(s,6H),2.20(d,J=6.5Hz,2H). 13 C NMR (125 MHz, CDCl 3)δ139.7,139.1,138.0,133.1,132.2,131.1,125.5,123.8,122.7,122.4,116.6,116.6,55.0,45.1,43.5,23.3.

[0217] Embodiment 29

[0218] Synthesis of compound 29

[0219]

[0220] 4-Formylphenyl sulfide (1.0 g, 4.7 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (187 mg, 0.47 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 15 equiv.) were added to replace oxygen and reacted at 50 °C for 3 hours. TLC detected that the reaction of the raw material was complete. The solvent was spin-dried and the mixture was washed with saturated sodium chloride aqueous solution. The mixture was extracted with ethyl acetate and separated by organic phase column chromatography to obtain viscous liquid compound 29 0.86 g (3.8 mmol, 80% yield).

[0221] The relevant characterization results of compound 29 are as follows:

[0222] 1 H NMR (500 MHz, CDCl 3 )δ10.03(s,1H),7.96(d,J=8.5Hz,2H),7.82(d,J=8.5Hz,2H),7.70–7.62(m,2H),7.48(dd,J=5.0,1.5Hz,3H). 13 C NMR (125 MHz, CDCl 3 )δ191.1,152.2,144.9,137.9,131.7,130.4,129.6,125.0,124.9.

[0223] Embodiment 30

[0224] Synthesis of compound 30

[0225]

[0226] N-acetyldibenzothiazine (1.0 g, 4.1 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2O (164 mg, 0.41 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 17 equiv.) were added to replace oxygen and reacted at room temperature for 3 hours. TLC detected that the reaction of the raw material was complete. The solvent was spin-dried and the mixture was washed with saturated sodium chloride aqueous solution. The mixture was extracted with ethyl acetate and separated by organic phase column chromatography to obtain viscous liquid compound 30 0.86 g (3.8 mmol, 80% yield).

[0227] The relevant characterization results of compound 30 are as follows:

[0228] 1 H NMR (500 MHz, CDCl 3 )δ7.81(dd,J=7.5,1.5Hz,2H),7.63(d,J=8.0Hz,2H),7.40–7.48(m,4H),2.29(s,3H). 13 C NMR (125 MHz, CDCl 3 )δ168.0,139.8,133.5,130.2,127.3,126.3,124.2,23.1.

[0229] Embodiment 31

[0230] Synthesis of compound 31

[0231]

[0232] 4-Chloromethylphenyl sulfide (1.0 g, 4.3 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (172 mg, 0.43 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 16 equiv.) were added to replace oxygen and reacted at 50 °C for 3 hours. TLC detected that the reaction of the raw material was complete. The solvent was spin-dried and the mixture was washed with saturated sodium chloride aqueous solution. The mixture was extracted with ethyl acetate and separated by organic phase column chromatography to obtain viscous liquid compound 31 0.91 g (3.7 mmol, 85% yield).

[0233] The relevant characterization results of compound 31 are as follows:

[0234] 1 H NMR (500 MHz, CDCl 3 )δ7.67–7.60(m,4H),7.51–7.42(m,5H),4.56(s,2H). 13 CNMR (125MHz, CDCl 3)δ145.8,145.3,140.4,131.2,129.4,129.4,125.1,124.7,45.2.

[0235] Embodiment 32

[0236] Synthesis of compound 32

[0237]

[0238] 4,6-Dimethyldibenzothiophene (1.0 g, 4.7 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (188 mg, 0.47 mmol, 10 mol%) and trifluoroacetic acid (4 mL, 51.0 mmol, 11 equiv.), replace oxygen, react at 50 ° C for 3 hours, TLC detection of the reaction of the raw materials is complete, the solvent is spin-dried, washed with saturated sodium chloride aqueous solution, extracted with ethyl acetate, and separated by organic phase column chromatography to obtain a viscous liquid compound 320.86 g (3.8 mmol, 80% yield).

[0239] The relevant characterization results of compound 32 are as follows:

[0240] 1 H NMR (500 MHz, CDCl 3 )δ7.60(d,J=7.5Hz,2H),7.46(t,J=7.5Hz,2H),7.23(d,J=7.5Hz,2H),2.74(s,6H). 13 C NMR (125 MHz, CDCl 3 )δ142.7,139.1,137.6,132.6,130.9,119.4,18.6.

[0241] Embodiment 33

[0242] Synthesis of compound 33

[0243]

[0244] 4-Aminoanisyl thioether (1.4 g, 10.0 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2O (400 mg, 1.0 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 7 equiv.) were added to replace oxygen, and the reaction was carried out at 50° C. for 3 hours. TLC detected that the reaction of the raw material was complete. The solvent was spin-dried, washed with saturated sodium chloride aqueous solution, extracted with ethyl acetate, and separated by organic phase column chromatography to obtain viscous liquid compound 33 0.85 g (4.3 mmol, 43% yield).

[0245] The relevant characterization results of compound 33 are as follows:

[0246] 1 H NMR (500 MHz, CDCl 3 )δ7.50–7.39(m,3H),7.22(d,J=8.5Hz,2H),2.45(s,3H),2.16(s,3H). 13 C NMR (125 MHz, CDCl 3 )δ168.4,135.5,133.6,127.9,120.6,24.5,16.6.

[0247] Embodiment 34

[0248] Synthesis of compound 34

[0249]

[0250] 3-Methyl(2-phenoxy)ethyl sulfide (3.0 g, 12.3 mol, 1.0 equiv.), Fe(NO 3 ) 3 .9H 2 O (480 mg, 1.2 mmol, 10 mol%) and acetic acid (4 mL, 70.0 mmol, 6 equiv.) were added to replace oxygen and reacted at 50 °C for 3 hours. TLC detected that the reaction of the raw material was complete. The solvent was spin-dried and the mixture was washed with saturated sodium chloride aqueous solution. The mixture was extracted with ethyl acetate and separated by organic phase column chromatography to obtain viscous liquid compound 33 2.9 g (11.3 mmol, 92% yield).

[0251] The relevant characterization results of compound 34 are as follows:

[0252] 1 H NMR (300 MHz, CDCl 3)δ7.41(s,1H),7.39–7.27(m,2H),7.17–7.22(m,3H),6.89(t,J=7.5Hz,1H),6.84–6.75( m,2H),4.44–4.29(m,1H),4.11(dt,J=10.2,5.1Hz,1H),3.04–3.13(m,2H),2.31(s,3H). 13 C NMR (75MHz, CDCl 3 )δ157.5,143.1,139.1,131.5,129.1,128.7,123.7,120.9,120.6,114.2,60.2,56.6,20.9.

[0253] The protection content of the present invention is not limited to the above embodiments. Without departing from the spirit and scope of the present invention, changes and advantages that can be thought of by those skilled in the art are included in the present invention and are protected by the attached claims.

Claims

1. A method for preparing sulfoxide compounds by catalytic oxidation of sulfide, characterized in that: Using sulfide as raw material, an oxidation reaction is carried out with oxygen under the action of a catalyst and an additive to selectively obtain sulfoxide compounds. The reaction process of the method is as follows: Among them, R 1 is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-formylphenyl, 4-formylphenyl, thiophene, thiazole, benzothiophene, benzothiazole, benzisothiazole, dibenzothiophene, phenoxathiol, phenothiazine, and thianthrene; R 2 is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-formylphenyl, 4-formylphenyl, thiophene, thiazole, benzothiophene, benzothiazole, benzisothiazole, dibenzothiophene, phenoxathiol, phenothiazine, and thianthrene; The catalyst is one or more of Fe(NO3)3, Al(NO3)3, KNO3, NaNO3, and Cu(NO3)2; The additive is one or more of trifluoroacetic acid, acetic acid, methanesulfonic acid, and p-toluenesulfonic acid; The molar amount of the catalyst is 10 mol% of the thioether; The molar amount of the additive is 10 equiv. of the thioether; The source of the oxygen is air; the temperature of the reaction is room temperature.

2. The method according to claim 1, characterized in that The reaction time is 2-36h.

3. The method according to claim 1, characterized in that The structural formula of the thioether is as follows:

4. The method according to claim 1, characterized in that The structural formula of the sulfoxide compound includes the following:

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