A method for synthesizing sulfur ylide compounds using electrochemistry

Abstract

The invention belongs to the field of organic electrosynthesis, and relates to a method for synthesizing a sulfur ylide compound by electrochemical synthesis, wherein a 10-phenyl phenothiazine analog, a 2-hydroxy-1,4-naphthoquinone analog and a catalyst are dissolved in an organic solvent to obtain a first mixed solution; an electrode is then inserted into the first mixed solution, a constant current is connected in an open system, and the reaction is stirred. After the reaction is completed, the reaction solution is post-treated to obtain a sulfur ylide product. The synthesis method of the present invention does not require an oxidant or a metal catalyst, is easy to operate, and is green and efficient. The sulfur ylide compound prepared by the present invention has the characteristics of high activity and a wide range of applications, and provides a novel reaction precursor for more organic reactions.

Description

Technical Field

[0001] The invention belongs to the field of organic electrosynthesis and relates to a method for synthesizing a sulfur ylide compound by electrochemistry. Background Art

[0002] Organosulfur compounds have long played a vital role in the development of organic synthesis and the construction of new chemical structures, among which the most prominent are organic compounds with sulfur as the central atom.

[0003] Since the first report of the Johnson-Corey-Chaykovsky reaction in 1960, sulfur-centered sulfur ylides have been the focus of chemists' research and have been the subject of countless studies over the past 100 years. Of particular interest is that sulfur ylide-type compounds can participate in a wide range of reactions due to their own structural and reactive characteristics. Sulfur ylides are zwitterionic compounds composed of a carbon anion and a neighboring positively charged sulfur atom, and can also act as nucleophiles with an easy leaving group. Sulfur ylides are widely used in many classic transformations of single-carbon synthons, many of which have become textbook knowledge. The most representative example is the introduction of sulfur ylides into electron-deficient π systems, followed by elimination, which is often used in the preparation of epoxides, aziridine compounds and cyclopropane compounds. In addition, there are [2,3]-single bond transfer, Stevens rearrangement, alkylation, and multi-step tandem cyclization to build complex structures. When traditional sulfur ylides or sulfonium inner salts participate in the synthesis reaction, they usually need to be prepared under the action of metal salts or strong oxidants before participating in the reaction. This type of reaction has the characteristics of high activity, which also causes some problems, such as poor operational safety, great harm, high toxicity, and environmental unfriendliness, as shown in references (J.Org.Chem., 1996, 61, 489-493; J.Org.Chem., 1996, 61, 8368-8369; Green Chem., 2010, 12, 2099-2119; Green Chem., 2014, 16, 69-72). As more and more organic synthesis practitioners are developing efficient, green, and stable new methods for synthesizing sulfur ylides, they are gradually developing towards high economic utilization, industrial applicability, and environmental friendliness. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a new method for synthesizing sulfur ylide compounds by electrochemistry in view of the deficiencies of the prior art. The method overcomes the problems of the traditional system such as harsh reaction conditions, the need for oxidants, metal catalysts, etc.

[0005] In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:

[0006] The invention discloses a method for synthesizing a sulfur ylide compound by electrochemical means, wherein a 10-phenyl phenothiazine analog, a 2-hydroxy-1,4-naphthoquinone analog and a catalyst are dissolved in an organic solvent to obtain a first mixed solution; then an electrode is inserted into the first mixed solution, a constant current is connected in an open system, and the reaction is stirred, and after the reaction is completed, the reaction solution is post-treated to obtain a sulfur ylide product;

[0007] Wherein, the structural formula of the 10-phenylphenothiazine analog is shown in Formula I, the structural formula of the 2-hydroxy-1,4-naphthoquinone analog is shown in Formula II, and the structural formula of the sulfur ylide product is shown in Formula III. The structural formulas of Formula I, Formula II, and Formula III are as follows:

[0008]

[0009] Wherein, R1, R2, and R3 are independently selected from any one of hydrogen, C1-C4 alkyl, halogen, unsubstituted or substituted aromatic ring, electron withdrawing group and electron donating group.

[0010] Preferably, R1 is selected from any one of hydrogen, C1-C4 alkyl, halogen, unsubstituted or substituted aromatic ring, nitro, cyano, trifluoromethyl, ester, alkoxy and thiomethyl; R2 is selected from any one of hydrogen, C1-C4 alkyl, halogen, unsubstituted or substituted aromatic ring, cyano, trifluoromethyl, acetyl, alkoxy and thiomethyl; R3 is selected from any one of hydrogen, C1-C4 alkyl, halogen, unsubstituted or substituted aromatic ring, cyano, trifluoromethyl, alkoxy and thiomethyl.

[0011] More preferably, R1 is selected from any one of hydrogen, methyl, tert-butyl, chlorine, bromine, phenyl, nitro, cyano and methoxy; R2 is selected from any one of hydrogen, methyl, chlorine, trifluoromethyl and methoxy; R3 is selected from any one of hydrogen, methyl and fluorine.

[0012] Specifically, the catalyst is any one or a combination of potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium phosphate, potassium carbonate, disodium hydrogen phosphate and sodium bicarbonate, preferably any one or a combination of potassium dihydrogen phosphate, potassium carbonate and sodium bicarbonate, more preferably potassium dihydrogen phosphate.

[0013] Specifically, the organic solvent is any one or a combination of dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, 1,2-dichloroethane, trifluoroethanol, hexafluoroisopropanol, methanol and ethanol, preferably any one or a combination of N,N-dimethylformamide, acetonitrile, methanol, ethanol, dimethyl sulfoxide and trifluoroethanol, and more preferably a mixed solvent of dimethyl sulfoxide and trifluoroethanol in a volume ratio of 7:1.

[0014] Specifically, in the first mixed solution, the concentration of the 10-phenylphenothiazine analog is 0.05-0.075 mmol / mL, the concentration of the 2-hydroxy-1,4-naphthoquinone analog is 0.0375-0.075 mmol / mL, and the concentration of the catalyst is 0.0375-0.0625 mmol / mL.

[0015] Preferably, in the first mixed solution, the concentration of the 10-phenylphenothiazine analog is 0.075 mmol / mL, the concentration of the 2-hydroxy-1,4-naphthoquinone analog is 0.075 mmol / mL, and the concentration of the catalyst is 0.05 mmol / mL.

[0016] Specifically, the positive electrode of the electrode is any one of a carbon cloth electrode, a carbon rod electrode, a foam carbon electrode and a platinum electrode, and the negative electrode is any one of an iron electrode, a nickel electrode and a platinum electrode.

[0017] Preferably, the positive electrode of the electrode is a carbon cloth electrode or a carbon rod electrode, and the negative electrode is a platinum electrode.

[0018] More preferably, the positive electrode of the electrode is a carbon cloth electrode, and the negative electrode is a platinum electrode.

[0019] Specifically, the constant current is 6-12 mA, preferably 10 mA.

[0020] Specifically, the stirring reaction has a reaction temperature of 25 to 80° C. and a reaction time of 3 to 7 hours.

[0021] Preferably, the stirring reaction has a reaction temperature of 45° C. and a reaction time of 5 h.

[0022] Wherein, the synthesis method of the 10-phenylphenothiazine analogue is referred to the prior art: Chemistry-A European Journal, 28(52), e202201322; 2022.

[0023] Wherein, the synthesis method of the 2-hydroxy-1,4-naphthoquinone analogue is referred to the prior art: Chemical Communications (Cambridge, United Kingdom), 55(16), 2348-2351; 2019.

[0024] Beneficial effects:

[0025] (1) The present invention adopts an electrochemical synthesis method, which significantly improves the reaction efficiency.

[0026] (2) The synthesis method of the present invention does not require an oxidant or a metal catalyst, is easy to operate, and is green and efficient.

[0027] (3) The sulfur ylide compound prepared by the present invention has the characteristics of high activity and wide application range, and provides a novel reaction precursor for more organic reactions. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments, and the above and / or other advantages of the present invention will become more clear.

[0029] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the product 3a in Example 1.

[0030] Figure 2 This is the hydrogen nuclear magnetic resonance spectrum of the product 3b in Example 11.

[0031] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of the product 3c in Example 12.

[0032] Figure 4 This is the hydrogen nuclear magnetic resonance spectrum of product 3d in Example 13.

[0033] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of the product 3e in Example 14.

[0034] Figure 6 This is the hydrogen nuclear magnetic resonance spectrum of the product 3f in Example 15.

[0035] Figure 7 This is the hydrogen nuclear magnetic resonance spectrum of the product 3g in Example 16.

[0036] Figure 8 This is the hydrogen nuclear magnetic resonance spectrum of the product 3h in Example 17.

[0037] Fig. 9 This is the hydrogen nuclear magnetic resonance spectrum of the product 3i in Example 18.

[0038] Fig.10 This is the hydrogen nuclear magnetic resonance spectrum of the product 3j in Example 19.

[0039] Fig.11 This is the hydrogen nuclear magnetic resonance spectrum of the product 3k in Example 20.

[0040] Fig.12 This is the hydrogen nuclear magnetic resonance spectrum of the product 31 in Example 21.

[0041] Fig.13 This is the hydrogen nuclear magnetic resonance spectrum of product 3m in Example 22.

[0042] Fig.14 This is the hydrogen nuclear magnetic resonance spectrum of product 3n in Example 23.

[0043] Fig.15 This is the hydrogen nuclear magnetic resonance spectrum of the product 3o in Example 24.

[0044] Fig.16 This is the reaction equation for the electrochemical synthesis of sulfur ylide compounds. DETAILED DESCRIPTION

[0045] The present invention can be better understood according to the following examples. However, it is easy for those skilled in the art to understand that the contents described in the examples are only used to illustrate the present invention, and should not and will not limit the present invention described in detail in the claims.

[0046] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0047] The specific reaction equation for the electrochemical synthesis of sulfur ylide compounds can be found in Fig.16 .

[0048] The synthesis method of the 10-phenylphenothiazine analogue used in the embodiments of the present invention refers to the prior art: Chemistry-A European Journal, 28(52), e202201322; 2022.

[0049] The synthesis method of 2-hydroxy-1,4-naphthoquinone analogs used in the embodiments of the present invention refers to the prior art: Chemical Communications (Cambridge, United Kingdom), 55(16), 2348-2351; 2019.

[0050] Among them, the sulfur ylide compounds shown in Table 1 are all products synthesized by the method of the present invention and confirmed by nuclear magnetic resonance characterization.

[0051] Table 1 Sulfur ylide compounds of the present invention

[0052]

[0053]

[0054] Table 2 Reactants of the present invention

[0055]

[0056]

[0057] Example 1: Synthesis of Compound 3a

[0058] 10-phenylphenothiazine 1a (0.6mmol, 3.0equiv), 2-hydroxy-1,4-naphthoquinone 2a (0.6mmol, 3.0equiv), potassium dihydrogen phosphate (0.4mmol, 2.0equiv), dimethyl sulfoxide (7mL) and trifluoroethanol (1mL) were weighed and mixed for reaction. The reaction temperature was controlled at 45°C. A carbon cloth electrode (35mm x 15mm) was used as the positive electrode, and a platinum electrode (10mm x10mm x 0.1mm) was used as the negative electrode. The constant current was controlled to be 10mA, and the reaction time was about 5h. The reaction progress was detected by TLC (petroleum ether: ethyl acetate = 2:3). After the reaction was completed, the reaction solution was extracted with ethyl acetate (50mL×3) and water (50mL×3), the organic phases were combined, dried over anhydrous sodium sulfate, and the crude product was concentrated and separated by silica gel column chromatography using petroleum ether / dichloromethane / ethyl acetate = 3:2:0.5 as the developing solvent to obtain the target product 3a with a yield of 89%. 1 HNMR (400MHz, Chloroform-d) δ8.21 (dd, J=7.9, 1.3Hz, 1H), 8.06 (dd, J=7.7, 1.3Hz, 1H), 7.80-7. 68(m,5H),7.66-7.54(m,4H),7.25-7.18(m,2H),7.04-6.97(m,2H),6.46(dd,J=8.8,1.0Hz,2H). 13 C NMR (101MHz, CDCl3) δ183.10,178.07,172.06,143.31,139.18,134.64,134.36,132.75,132.04,131.4 3,131.10,130.46,129.63,127.40,126.93,122.52,116.99,107.66,103.78.HRMS(ESI-TOF)Calcdfor C 28 H 18 NO3S[M+H] + :448.1002; found:448.1006. Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the product 3a in Example 1.

[0059] Example 2: Synthesis of Compound 3a - Solvent Screening

[0060] 10-phenylphenothiazine 1a (0.6mmol, 3.0equiv), 2-hydroxy-1,4-naphthoquinone 2a (0.6mmol, 3.0equiv), potassium dihydrogen phosphate (0.4mmol, 2.0equiv), acetonitrile (7mL) and trifluoroethanol (1mL) were weighed and mixed for reaction. The reaction temperature was controlled at 45°C. A carbon cloth electrode (35mm x 15mm) was used as the positive electrode, and a platinum electrode (10mm x10mm x0.1mm) was used as the negative electrode. The constant current was controlled to be 10mA, and the reaction time was about 5h. The reaction progress was detected by TLC (petroleum ether: ethyl acetate = 2:3). After the reaction was completed, the reaction solution was extracted with ethyl acetate (50mL×3) and water (50mL×3), the organic phases were combined, dried over anhydrous sodium sulfate, and the crude product was concentrated and separated by silica gel column chromatography using petroleum ether / dichloromethane / ethyl acetate = 3:2:0.5 as the developing solvent to obtain the target product 3a with a yield of 41%.

[0061] Example 3: Synthesis of Compound 3a - Solvent Screening

[0062] 10-phenylphenothiazine 1a (0.6 mmol, 3.0 equiv), 2-hydroxy-1,4-naphthoquinone 2a (0.6 mmol, 3.0 equiv), potassium dihydrogen phosphate (0.4 mmol, 2.0 equiv), N,N-dimethylformamide (7 mL) and trifluoroethanol (1 mL) were weighed and mixed for reaction. The reaction temperature was controlled at 45°C. A carbon cloth electrode (35 mm x 15 mm) was used as the positive electrode, and a platinum electrode (10 mm x 10 mm x 0.1 mm) was used as the negative electrode. The constant current was controlled to be 10 mA, and the reaction time was about 5 h. The reaction progress was detected by TLC (petroleum ether: ethyl acetate = 2:3). After the reaction, the reaction solution was extracted with ethyl acetate (50 mL×3) and water (50 mL×3), the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated. The crude product was separated by silica gel column chromatography using petroleum ether / dichloromethane / ethyl acetate = 3:2:0.5 as a developing solvent to obtain the target product 3a with a yield of 57%.

[0063] Example 4: Synthesis of Compound 3a - Solvent Screening

[0064] 10-phenylphenothiazine 1a (0.6mmol, 3.0equiv), 2-hydroxy-1,4-naphthoquinone 2a (0.6mmol, 3.0equiv), potassium dihydrogen phosphate (0.4mmol, 2.0equiv), dimethyl sulfoxide (7mL) and methanol (1mL) were weighed and mixed for reaction. The reaction temperature was controlled at 45°C. A carbon cloth electrode (35mm x 15mm) was used as the positive electrode, and a platinum electrode (10mm x10mm x 0.1mm) was used as the negative electrode. The constant current was controlled to be 10mA, and the reaction time was about 5h. The reaction progress was detected by TLC (petroleum ether: ethyl acetate = 2:3). After the reaction was completed, the reaction solution was extracted with ethyl acetate (50mL×3) and water (50mL×3), the organic phases were combined, dried over anhydrous sodium sulfate, and the crude product was concentrated and separated by silica gel column chromatography using petroleum ether / dichloromethane / ethyl acetate = 3:2:0.5 as the developing solvent to obtain the target product 3a with a yield of 73%.

[0065] Example 5: Synthesis of Compound 3a - Solvent Screening

[0066] 10-phenylphenothiazine 1a (0.6mmol, 3.0equiv), 2-hydroxy-1,4-naphthoquinone 2a (0.6mmol, 3.0equiv), potassium dihydrogen phosphate (0.4mmol, 2.0equiv), dimethyl sulfoxide (7mL) and ethanol (1mL) were weighed and mixed for reaction. The reaction temperature was controlled at 45°C. A carbon cloth electrode (35mm x 15mm) was used as the positive electrode, and a platinum electrode (10mm x10mm x 0.1mm) was used as the negative electrode. The constant current was controlled to be 10mA, and the reaction time was about 5h. The reaction progress was detected by TLC (petroleum ether: ethyl acetate = 2:3). After the reaction was completed, the reaction solution was extracted with ethyl acetate (50mL×3) and water (50mL×3), the organic phases were combined, dried over anhydrous sodium sulfate, and the crude product was concentrated and separated by silica gel column chromatography using petroleum ether / dichloromethane / ethyl acetate = 3:2:0.5 as the developing solvent to obtain the target product 3a with a yield of 73%.

[0067] Example 6: Synthesis of Compound 3a - Catalyst Screening

[0068] 10-phenylphenothiazine 1a (0.6mmol, 3.0equiv), 2-hydroxy-1,4-naphthoquinone 2a (0.6mmol, 3.0equiv), potassium dihydrogen phosphate (0.4mmol, 2.0equiv), dimethyl sulfoxide (7mL) and trifluoroethanol (1mL) were weighed and mixed for reaction. The reaction temperature was controlled at 45°C. A carbon cloth electrode (35mm x 15mm) was used as the positive electrode, and a platinum electrode (10mm x10mm x 0.1mm) was used as the negative electrode. The constant current was controlled to be 10mA, and the reaction time was about 5h. The reaction progress was detected by TLC (petroleum ether: ethyl acetate = 2:3). After the reaction was completed, the reaction solution was extracted with ethyl acetate (50mL×3) and water (50mL×3), the organic phases were combined, dried over anhydrous sodium sulfate, and the crude product was concentrated and separated by silica gel column chromatography using petroleum ether / dichloromethane / ethyl acetate = 3:2:0.5 as the developing solvent to obtain the target product 3a with a yield of 37%.

[0069] Example 7: Synthesis of Compound 3a - Catalyst Screening

[0070] 10-phenylphenothiazine 1a (0.6mmol, 3.0equiv), 2-hydroxy-1,4-naphthoquinone 2a (0.6mmol, 3.0equiv), potassium carbonate (0.4mmol, 2.0equiv), dimethyl sulfoxide (7mL) and trifluoroethanol (1mL) were weighed and mixed for reaction. The reaction temperature was controlled at 45°C. A carbon cloth electrode (35mm x 15mm) was used as the positive electrode, and a platinum electrode (10mm x10mm x 0.1mm) was used as the negative electrode. The constant current was controlled to be 10mA, and the reaction time was about 5h. The reaction progress was detected by TLC (petroleum ether: ethyl acetate = 2:3). After the reaction was completed, the reaction solution was extracted with ethyl acetate (50mL×3) and water (50mL×3), the organic phases were combined, dried over anhydrous sodium sulfate, and the crude product was concentrated and separated by silica gel column chromatography using petroleum ether / dichloromethane / ethyl acetate = 3:2:0.5 as the developing solvent to obtain the target product 3a with a yield of 41%.

[0071] Example 8: Synthesis of Compound 3a - Catalyst Screening

[0072] 10-phenylphenothiazine 1a (0.6mmol, 3.0equiv), 2-hydroxy-1,4-naphthoquinone 2a (0.6mmol, 3.0equiv), sodium bicarbonate (0.4mmol, 2.0equiv), dimethyl sulfoxide (7mL) and trifluoroethanol (1mL) were weighed and mixed for reaction. The reaction temperature was controlled at 45°C. A carbon cloth electrode (35mm x 15mm) was used as the positive electrode, and a platinum electrode (10mm x10mm x 0.1mm) was used as the negative electrode. The constant current was controlled to be 10mA, and the reaction time was about 5h. The reaction progress was detected by TLC (petroleum ether: ethyl acetate = 2:3). After the reaction was completed, the reaction solution was extracted with ethyl acetate (50mL×3) and water (50mL×3), the organic phases were combined, dried over anhydrous sodium sulfate, and the crude product was concentrated and separated by silica gel column chromatography using petroleum ether / dichloromethane / ethyl acetate = 3:2:0.5 as the developing solvent to obtain the target product 3a with a yield of 53%.

[0073] Example 9: Synthesis of Compound 3a - Cathode Screening

[0074] 10-phenylphenothiazine 1a (0.6 mmol, 3.0 equiv), 2-hydroxy-1,4-naphthoquinone 2a (0.6 mmol, 3.0 equiv), potassium dihydrogen phosphate (0.4 mmol, 2.0 equiv), dimethyl sulfoxide (7 mL) and trifluoroethanol (1 mL) were weighed and mixed for reaction. The reaction temperature was controlled at 45 °C. A carbon rod electrode (5 mm x 5 mm x 60 mm) was used as the positive electrode, and a platinum electrode (10 mm x 10 mm x 0.1 mm) was used as the negative electrode. The constant current was controlled to be 10 mA, and the reaction time was about 5 h. The reaction progress was detected by TLC (petroleum ether: ethyl acetate = 2:3). After the reaction, the reaction solution was extracted with ethyl acetate (50 mL×3) and water (50 mL×3), the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated. The crude product was separated by silica gel column chromatography using petroleum ether / dichloromethane / ethyl acetate = 3:2:0.5 as a developing solvent to obtain the target product 3a with a yield of 49%.

[0075] Example 10: Synthesis of compound 3a - positive electrode and negative electrode screening

[0076] 10-phenylphenothiazine 1a (0.6 mmol, 3.0 equiv), 2-hydroxy-1,4-naphthoquinone 2a (0.6 mmol, 3.0 equiv), potassium dihydrogen phosphate (0.4 mmol, 2.0 equiv), dimethyl sulfoxide (7 mL) and trifluoroethanol (1 mL) were weighed and mixed for reaction. The reaction temperature was controlled at 45 °C. A platinum electrode (10 mm x 10 mm x 0.1 mm) was used as the positive electrode, and an iron electrode (10 mm x 10 mm x 0.1 mm) was used as the negative electrode. The constant current was controlled to be 10 mA, and the reaction time was about 5 h. The reaction progress was detected by TLC (petroleum ether: ethyl acetate = 2:3). After the reaction, the reaction solution was extracted with ethyl acetate (50 mL×3) and water (50 mL×3), and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated. The crude product was separated by silica gel column chromatography using petroleum ether / dichloromethane / ethyl acetate = 3:2:0.5 as a developing solvent to obtain the target product 3a with a yield of 20%.

[0077] Example 11: Synthesis of Compound 3b

[0078] The method is the same as that of Example 1, except that compounds 1b and 2a are involved in the reaction. The yield is 74%, and product 3b is obtained after column chromatography separation. 1 H NMR(400MHz,Chloroform-d)δ8.20(d,J=7.7Hz,1H),8.05(d,J=7.6Hz,1H),7.75-7.62(m,5H),7.55 (d,J=8.4Hz,3H),7.23(t,J=8.0Hz,2H),6.99(t,J=7.5Hz,2H),6.49(d,J=8.5Hz,2H),1.45(s,9H). 13 C NMR (101MHz, CDCl3) δ183.10,178.03,172.06,152.80,143.46,136.38,134.70,134.31,132.68,132.00,13 0.39,130.33,128.25,127.38,126.90,122.40,117.10,107.65,103.80,35.00,31.46.HRMS(ESI-TOF)Calcd forC 32 H 26 NO3S[M+H] + :504.1628; found:504.1628. Figure 2 This is the hydrogen nuclear magnetic resonance spectrum of the product 3b in Example 11.

[0079] Example 12: Synthesis of Compound 3c

[0080] The method is the same as that in Example 1, except that compounds 1c and 2a are involved in the reaction, and the yield is 76%. Product 3c is obtained after column chromatography separation. 1 H NMR(400MHz,Chloroform-d)δ8.22(dd,J=7.9,1.3Hz,1H),8.06(dd,J=7.7,1.3Hz,1H),7.94(d,J=8.5Hz,2H),7.83(d,J=7.9Hz, 2H),7.75-7.68(m,3H),7.61-7.51(m,5H),7.47-7.42(m,1H),7.28-7.22(m,2H),7.05-6.99(m,2H),6.57(dd,J=8.7,1.1Hz,2H). 13 C NMR (101MHz, CDCl3) δ183.12,178.10,172.08,143.34,142.54,139.87,138.24,134.65,134.37,132.80,132.06,131 .43,130.50,130.02,129.08,128.09,127.43,127.32,126.95,122.58,117.07,107.65,103.87.HRMS(ESI-TOF)Calcd for C 34 H 22 NO3S[M+H] + :524.1315; found:524.1321. Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of the product 3c in Example 12.

[0081] Example 13: Synthesis of Compound 3d

[0082] The method is the same as that of Example 1, except that compounds 1d and 2a are involved in the reaction, and the yield is 73%. Product 3d is obtained after column chromatography separation. 1 H NMR (400MHz, Chloroform-d) δ8.21 (dd, J=7.7, 1.3Hz, 1H), 8.05 (dd, J=7.8, 1.3Hz, 1H), 7.77-7. 69(m,5H),7.61-7.55(m,3H),7.28-7.22(m,2H),7.06-7.00(m,2H),6.47(dd,J=8.7,1.1Hz,2H). 13C NMR (101MHz, CDCl3) δ183.06,178.11,172.03,143.13,137.66,135.70,134.57,134.41,132.87,132.71, 132.11,132.02,131.77,130.60,127.44,126.95,122.79,116.81,107.49,104.01.HRMS(ESI-TOF)Calcd forC 28 H 17 ClNO3S[M+H] + :482.0612; found:482.0611. Figure 4 This is the hydrogen nuclear magnetic resonance spectrum of product 3d in Example 13.

[0083] Example 14: Synthesis of Compound 3e

[0084] The method is the same as that in Example 1, except that compounds 1e and 2a are involved in the reaction, and the yield is 77%. Product 3e is obtained after column chromatography separation. 1 H NMR(400MHz,Chloroform-d)δ8.21(dd,J=7.8,1.3Hz,1H),8.05(dd,J=7.7,1.3Hz,1H),7.72-7.63(m,3 H),7.59-7.52(m,3H),7.26-7.19(m,4H),7.02-6.97(m,2H),6.52(dd,J=8.7,1.1Hz,2H),3.94(s,3H). 13 C NMR (101MHz, CDCl3) δ183.11,178.04,172.03,160.15,143.67,134.66,134.32,132.71,132.07,132.00 ,131.63,130.41,127.37,126.92,122.43,117.06,116.45,107.69,103.81,55.66.HRMS(ESI-TOF)Calcd forC 29 H 20 NO4S[M+H] + :478.1108; found:478.1110. Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of the product 3e in Example 14.

[0085] Example 15: Synthesis of Compound 3f

[0086] The method is the same as that in Example 1, except that compounds 1f and 2a are involved in the reaction, and the yield is 71%. Product 3f is obtained after column chromatography separation. 1 H NMR(400MHz,Chloroform-d)δ8.21(dd,J=7.8,1.3Hz,1H),8.09-7.98(m,5H),7.71(td,J=7.5,1 .3Hz,1H),7.63-7.55(m,3H),7.29-7.24(m,2H),7.10-7.04(m,2H),6.37(dd,J=8.7,1.0Hz,2H). 13 C NMR (101MHz, CDCl3) δ182.97,178.14,172.05,143.41,142.68,135.39,134.48,133.02,132.80,132.20, 131.99,130.81,127.48,126.95,123.20,117.86,116.57,113.97,107.19,104.32.HRMS(ESI-TOF)Calcd for C 29 H 17 N2O3S[M+H] + :473.0954; found:473.0965. Figure 6 This is the hydrogen nuclear magnetic resonance spectrum of the product 3f in Example 15.

[0087] Example 16: Synthesis of Compound 3g

[0088] The method is the same as that of Example 1, except that compounds 1g and 2a are involved in the reaction, and the yield is 70%. Product 3g is obtained after column chromatography separation. 1 H NMR(400MHz,Chloroform-d)δ8.14(dd,J=7.8,1.3Hz,1H),8.10-8.05(m,1H),8.02-7.96(m,1H),7.66-7.60(m,1H), 7.54-7.34(m,6H),7.19-6.98(m,2H),6.97-6.87(m,2H),6.26(dd,J=8.7,1.1Hz,2H),2.57(s,0.5H),1.97(s,2.5H). 13C NMR (101MHz, CDCl3) δ183.12,178.05,172.05,142.20,141.57,139.96,137.83,13 7.79,137.61,134.67,134.35,134.32,133.12,132.85,132.07,132.03,131.50,13 1.45,130.65,130.17,129.94,129.91,129.76,128.85,127.41,126.93,126.77,12 2.53,122.47,116.24,107.83,104.82,103.79,17.51,17.30.HRMS(ESI-TOF)Calcd for C 29 H 20 NO3S[M+H] + :462.1158; found:462.1177. Figure 7 This is the hydrogen nuclear magnetic resonance spectrum of the product 3g in Example 16.

[0089] Example 17: Synthesis of Compound 3h

[0090] The method was the same as that in Example 1, except that compounds 1h and 2a were involved in the reaction. The yield was 71%, and product 3h was obtained after column chromatography separation. 1 H NMR(400MHz,Chloroform-d)δ8.38(dd,J=7.9,1.7Hz,1H),8.22(dd,J=7.8,1.3Hz,1H),8.06(dd,J=7.7,1.3Hz,1H),7.89(dd,J=8.1,1.4Hz ,1H),7.72(tt,J=7.6,1.7Hz,2H),7.63-7.56(m,3H),7.51(td,J=7.7,1.5Hz,1H),7.31-7.26(m,2H),7.09-7.00(m,2H),6.38-6.30(m,2H). 13 C NMR (101MHz, CDCl3) δ183.11,178.13,172.02,141.88,138.24,134.62,134.40,134.05,133.79,133.06,133.0 1,132.08,131.35,130.63,127.43,126.96,125.64,122.94,116.53,107.55,104.13.HRMS(ESI-TOF)Calcdfor C 28 H 17 BrNO3S[M+H]+ :526.0107; found:526.0109. Figure 8 This is the hydrogen nuclear magnetic resonance spectrum of the product 3h in Example 17.

[0091] Example 18: Synthesis of Compound 3i

[0092] The method is the same as that in Example 1, except that compounds 1i and 2a are involved in the reaction, and the yield is 81%. Product 3i is obtained after column chromatography separation. 1 H NMR(400MHz,Chloroform-d)δ8.56(d,J=7.9Hz,1H),8.31(dd,J=8.1,1.5Hz,1H),8.23(dd,J=7.8,1.3Hz,1H),8.09-8.02(m,2H),7.85(t d,J=8.1,1.6Hz,1H),7.72(td,J=7.6,1.4Hz,1H),7.62-7.56(m,3H),7.29-7.24(m,2H),7.10-7.03(m,2H),6.31(dd,J=8.6,1.1Hz,2H). 13 C NMR (101MHz, CDCl3) δ183.12,178.14,171.99,148.53,142.26,137.36,134.88,134.53,134.49,133.13,132.65,1 32.16,132.02,131.27,130.75,127.43,127.00,125.89,123.25,116.28,107.40,104.55.HRMS(ESI-TOF)Calcdfor C 28 H 17 N2O5S[M+H] + :493.0853; found:493.0852. Fig. 9 This is the hydrogen nuclear magnetic resonance spectrum of the product 3i in Example 18.

[0093] Example 19: Synthesis of Compound 3j

[0094] The method is the same as that of Example 1, except that compounds 1j and 2a are involved in the reaction, and the yield is 82%. Product 3j is obtained after column chromatography separation. 1H NMR(400MHz,Chloroform-d)δ8.20(dd,J=7.7,1.3Hz,1H),8.04(dd,J=7.7,1.3Hz,1H),7.79-7.66(m,5H),7.65-7.60(m,1H),7.59-7.53(m,2H),7.44 (d,J=8.0Hz,1H),7.24-7.16(m,1H),7.02-6.95(m,1H),6.83(dd,J=8.1,1 .6Hz,1H),6.43(dd,J=8.7,1.1Hz,1H),6.24(d,J=1.6Hz,1H),2.15(s,3H). 13 C NMR (101MHz, CDCl3) δ183.14,178.03,172.02,143.74,143.36,143.22,139.25,134.69,134.29,132.63,132.04,131.96,131.37,131 .13,130.46,130.26,129.58,127.33,126.89,123.77,122.35,117.26,116.99,107.96,103.96,100.63,21.97.HRMS(ESI-TOF)Calcd for C 29 H 20 NO3S[M+H] + :462.1158; found:462.1171. Fig.10 This is the hydrogen nuclear magnetic resonance spectrum of the product 3j in Example 19.

[0095] Example 20: Synthesis of Compound 3k

[0096] The method is the same as that in Example 1, except that compounds 1k and 2a are involved in the reaction, and the yield is 80%. Product 3k is obtained after column chromatography separation. 1 H NMR(400MHz,Chloroform-d)δ8.21(dd,J=7.9,1.3Hz,1H),8.07(dd,J=7.7,1.3Hz,1H),7.76(d,J=4.7Hz,4H),7.72(td,J=7.8,1.5Hz,1H),7.6 8-7.63(m,1H),7.62-7.54(m,2H),7.50(d,J=8.4Hz,1H),7.26-7.22(m, 1H),7.07-7.02(m,1H),6.98(dd,J=8.4,2.0Hz,1H),6.47-6.42(m,2H). 13C NMR (101MHz, CDCl3) δ182.90,178.10,172.14,144.17,142.81,139.17,138.63,134.55,134.42,132.94,132.18,132.05,131.66, 131.51,130.83,130.49,130.03,127.50,126.93,123.12,122.76,117.27,116.75,107.35,104.09,102.14.HRMS(ESI-TOF)Calcd for C 28 H 17 ClNO3S[M+H] + :482.0612; found:482.0615. Fig.11 This is the hydrogen nuclear magnetic resonance spectrum of the product 3k in Example 20.

[0097] Example 21: Synthesis of Compound 31

[0098] The method is the same as that in Example 1, except that compounds 11 and 2a are involved in the reaction. The yield is 86%, and product 31 is obtained after column chromatography separation. 1 H NMR(400MHz,Chloroform-d)δ8.21(dd,J=7.8,1.3Hz,1H),8.05(dd,J=7.8,1.3Hz,1H),7.79-7.67(m,5H),7.64-7.54(m,3H),7.49(d,J=8.8 Hz,1H),7.24-7.18(m,1H),7.03-6.97(m,1H),6.59(dd,J=8.8,2.5Hz,1H),6.45(dd,J=8.7,1.1Hz,1H),5.94(d,J=2.5Hz,1H),3.60(s,3H). 13 C NMR (101MHz, CDCl3) δ183.21,178.06,171.98,162.98,144.92,143.13,139.21,134.68,134.30,132.62,132.03,131.97,131.94,13 1.38,131.03,130.48,129.66,127.34,126.88,122.46,117.01,109.04,108.27,104.34,102.56,95.22,55.33.HRMS(ESI-TOF)Calcd for C 29 H 20 NO4S[M+H] +:478.1108; found:478.1111. Fig.12 This is the hydrogen nuclear magnetic resonance spectrum of the product 31 in Example 21.

[0099] Example 22: Synthesis of Compound 3m

[0100] The method is the same as that in Example 1, except that compounds 1m and 2a are involved in the reaction, and the yield is 82%. Product 3m is obtained after column chromatography separation. 1 H NMR(400MHz,Chloroform-d)δ8.22(dd,J=7.8,1.3Hz,1H),8.08(dd,J=7.6,1.3Hz,1H),7.79-7.73(m,4H),7.73-7 .65(m,3H),7.63-7.56(m,2H),7.30-7.20(m,2H),7.10-7.04(m,1H),6.68(d,J=1.8Hz,1H),6.49(d,J=8.6Hz,1H). 13 C NMR (101MHz, CDCl3) δ182.78,178.10,172.19,143.58,142.86,138.40,135.08,134 .75,134.47(d,J=2.9Hz),134.09,133.12,132.78,132.27,132.04,131.77,131.59, 131.32,130.74,130.48,130.21,130.15,127.57,126.98,126.92,124.21,123.40, 121.49, 118.57 (q, J = 3.4Hz), 117.38, 113.63 (q, J = 4.2Hz), 107.22, 106.89, 103.89. 19 F NMR(376MHz,CDCl3)δ-63.70.HRMS(ESI-TOF)Calcd for C 29 H 17 F3NO3S[M+H] + :516.0876; found:516.0884. Fig.13 This is the hydrogen nuclear magnetic resonance spectrum of product 3m in Example 22.

[0101] Example 23: Synthesis of Compound 3n

[0102] The method is the same as that in Example 1, except that compounds 1a and 2b are involved in the reaction. The yield is 76%, and product 3n is obtained after column chromatography separation. 1H NMR(400MHz,Chloroform-d)δ8.01(d,J=7.9Hz,1H),7.77(d,J=1.7Hz,1H),7.71-7.60(m,4H),7.53(tt,J=7.1,1.6Hz,1H),7.47(d d,J=8.0,1.6Hz,2H),7.41(dd,J=8.0,1.8Hz,1H),7.16-7.09(m,2H),6.95-6.88(m,2H),6.37(dd,J=8.7,1.1Hz,2H),2.33(s,3H). 13 C NMR (101MHz, CDCl3) δ183.37,178.21,172.18,143.29,142.78,139.20,135.13,132.68,132.28,131.91,131 .41,131.12,130.45,129.61,127.73,127.03,122.48,116.97,107.26,103.93,21.44.HRMS(ESI-TOF)Calcd for C 29 H 20 NO3S[M+H] + :462.1158; found:462.1204. Fig.14 This is the hydrogen nuclear magnetic resonance spectrum of product 3n in Example 23.

[0103] Example 24: Synthesis of Compound 3o

[0104] The method was the same as that in Example 1, except that compounds 1a and 2c were involved in the reaction. The yield was 71%, and product 3o was obtained after column chromatography separation. 1 H NMR(400MHz,Chloroform-d)δ8.23(dd,J=8.6,5.3Hz,1H),7.78-7.68(m,5H),7.66-7.60(m,1H),7.56(dd,J=7 .9,1.5Hz,2H),7.37(td,J=8.2,2.7,2Hz,1H),7.26-7.19(m,2H),7.01(t,J=7.5Hz,2H),6.47(d,J=8.6Hz,2H). 13CNMR(101MHz, CDCl3)δ182.19,177.05,171.69,166.26,163.73,143.33,139.13,134.24(d,J=7.2Hz),132.83,131.45,1 31.04,130.99,130.45,129.83(d,J=8.3Hz),129.67,122.57,121.51,121.29,117.02,113.81,113.58,107.51,103.57. 19 F NMR(376MHz,CDCl3)δ-105.90.HRMS(ESI-TOF)Calcd for C 28 H 17 FNO3S[M+H] + :466.0908; found:466.0908. Fig.15 This is the hydrogen nuclear magnetic resonance spectrum of the product 3o in Example 24.

[0105] Example 25: Necessity of Electric Current

[0106] 10-phenylphenothiazine 1a (0.6mmol, 3.0equiv), 2-hydroxy-1,4-naphthoquinone 2a (0.6mmol, 3.0equiv), potassium dihydrogen phosphate (0.4mmol, 2.0equiv), dimethyl sulfoxide (7mL) and trifluoroethanol (1mL) were weighed and mixed for reaction. The reaction temperature was controlled at 45°C. A carbon cloth electrode (35mm x 15mm) was used as the positive electrode, and a platinum electrode (10mm x10mm x 0.1mm) was used as the negative electrode. No current was connected. The reaction time was about 5h. The reaction progress was monitored by TLC (petroleum ether: ethyl acetate = 2:3), and the target product 3a was not monitored.

[0107] The present invention provides a method and method for synthesizing sulfur ylide compounds by electrochemical method. There are many methods and ways to realize the technical solution. The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the protection scope of the present invention. All components not specified in this embodiment can be implemented by existing technologies.

Claims

1. A method for synthesizing a sulfur ylide compound using electrochemistry, characterized in that: Dissolving a 10-phenylphenothiazine analog, a 2-hydroxy-1,4-naphthoquinone analog and a catalyst in an organic solvent to obtain a first mixed solution; then inserting an electrode into the first mixed solution, connecting a constant current in an open system, stirring the reaction, and after the reaction is completed, post-treating the reaction solution to obtain a sulfur ylide product; Wherein, the structural formula of the 10-phenylphenothiazine analog is shown in Formula I, the structural formula of the 2-hydroxy-1,4-naphthoquinone analog is shown in Formula II, and the structural formula of the sulfur ylide product is shown in Formula III. The structural formulas of Formula I, Formula II, and Formula III are as follows: Wherein, R1 is selected from any one of hydrogen, C1-C4 alkyl, halogen, unsubstituted or substituted aromatic ring, nitro, cyano, trifluoromethyl, ester, alkoxy and thiomethyl; R2 is selected from any one of hydrogen, C1-C4 alkyl, halogen, unsubstituted or substituted aromatic ring, cyano, trifluoromethyl, acetyl, alkoxy and thiomethyl; R3 is selected from any one of hydrogen, C1-C4 alkyl, halogen, unsubstituted or substituted aromatic ring, cyano, trifluoromethyl, alkoxy and thiomethyl.

2. The method according to claim 1, characterized in that R1 is selected from any one of hydrogen, methyl, tert-butyl, chlorine, bromine, phenyl, nitro, cyano and methoxy; R2 is selected from any one of hydrogen, methyl, chlorine, trifluoromethyl and methoxy; R3 is selected from any one of hydrogen, methyl and fluorine.

3. The method according to claim 1, characterized in that The catalyst is any one or a combination of potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium phosphate, potassium carbonate, disodium hydrogen phosphate and sodium bicarbonate.

4. The method according to claim 1, characterized in that: The organic solvent is any one or a combination of dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, 1,2-dichloroethane, trifluoroethanol, hexafluoroisopropanol, methanol and ethanol.

5. The method according to claim 1, characterized in that In the first mixed solution, the concentration of the 10-phenylphenothiazine analog is 0.05-0.075 mmol / mL, the concentration of the 2-hydroxy-1,4-naphthoquinone analog is 0.0375-0.075 mmol / mL, and the concentration of the catalyst is 0.0375-0.0625 mmol / mL.

6. The method according to claim 1, characterized in that The electrodes include a positive electrode selected from any one of a carbon cloth electrode, a carbon rod electrode, a foamed carbon electrode and a platinum electrode, and a negative electrode selected from any one of an iron electrode, a nickel electrode and a platinum electrode.

7. The method according to claim 1, characterized in that The constant current is 6-12 mA.

8. The method according to claim 1, characterized in that The stirring reaction has a reaction temperature of 25 to 80° C. and a reaction time of 3 to 7 hours.

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