CN110846676B - Electrochemical synthesis method of chloroethyl sulfoxide compound - Google Patents
Electrochemical synthesis method of chloroethyl sulfoxide compound Download PDFInfo
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Abstract
The invention discloses an electrochemical synthesis method of chloroethyl sulfoxide compounds. The method comprises the steps of carrying out reaction in an undivided electrolytic tank, dissolving aryl thiophenol compounds, 1, 2-dichloroethane and electrolyte in a solvent to obtain a reaction solution, adding the reaction solution into the electrolytic tank, inserting an electrode into the reaction solution, connecting constant current in a proper gas atmosphere, stirring for reaction, and carrying out column chromatography separation after the reaction is finished to obtain chloroethyl sulfoxide.
Description
Technical Field
The invention belongs to the technical field of synthesis of pharmaceutical and chemical intermediates, and particularly relates to an electrochemical synthesis method of chloroethyl sulfoxide compounds.
Background
The sulfoxide and the derivatives thereof are used as very important intermediates and have important functions in the industries of medicine, chemical industry, pesticide, organic synthesis and the like. In particular, in the field of medicine, the well-known proton pump inhibitors for the treatment of gastric ulcers, omeprazole and lansoprazole, among others, also belong to the sulfoxide group of drugs. After the intensive research and structural modification of other sulfoxide compounds, a series of anti-tumor, anti-virus, anti-HIV and other medicines are also developed. Therefore, its efficient synthesis is one of the hot spots of the current research.
The conventional method for preparing sulfoxides is via thiol or thioether oxidation. For example, Brinksma project group 2001 reports a method for synthesizing sulfoxide under the catalysis of Mn (III) complex by taking benzyl sulfide as a raw material and hydrogen peroxide as an oxidant (Tetrahedron Letters,2001,42, 4049-. In 2005, the Velusamy project group reported a method for oxidizing sulfide into sulfoxide with copper (II) complex and hydrogen peroxide (Tetrahedron Letters,2005,46, 3819-3822), which can improve the selectivity and conversion rate of reaction after adding TEMPO in a mixed manner, and the copper (II) complex can be recycled. However, these methods are less sustainable because they require stoichiometric amounts of metal complexes as sacrificial acceptors for electrons.
In recent years, the selection of catalysts has shifted from metal complexes to nano-mesoporous materials. The Kiumars topic group uses SBA-15-PR-SO3H(Catalysis Science&Technology,2011,1,389-393.), is used as a nano reactor to catalytically oxidize sulfide into sulfoxide at 40 ℃, and has good yield. The Nikoorazm group successfully used H in the absence of a solvent using Si-MCM-41 as a catalyst, which is a vo (IV) complex2O2Several types of aryl thiophenols and aliphatic thiols are oxidized to the corresponding sulfoxides.
Chloroethyl sulfoxide, an important intermediate raw material, was used to prepare sitafloxacin, a quinolone antibacterial drug (j. org. chem.2014,79,15,7226-. The common method for preparing chloroethyl sulfoxide is to generate thiophenol and 1-chloro-2-bromoethane through two-step reaction (EP2277872,2016, B1), and then to oxidize sulfide into chloroethyl sulfoxide by using nano-scale mesoporous sodium iron hydroxy phosphate loaded with gold and hydrogen peroxide in methanol solvent at 60 ℃ (Catalysis Science and Technology,2016,6-7, 2055-2059).
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an electrochemical synthesis method of chloroethyl sulfoxide compounds, which is characterized in that thiophenol compounds, 1, 2-dichloroethane and electrolyte are dissolved in an organic solvent and subjected to oxidative coupling reaction under the action of current to generate chloroethyl sulfoxide.
The technical scheme adopted by the invention is as follows:
a synthetic method of chloroethyl sulfoxide compounds comprises the following steps: dissolving aryl thiophenol compound shown in formula (II), 1, 2-Dichloroethane (DCE) and electrolyte in a solvent to obtain a reaction solution, adding the reaction solution into an electrolytic bath, inserting an electrode into the reaction solution in a proper gas atmosphere, switching on constant current, stirring and reacting at a proper temperature, and after the reaction is finished, performing column chromatography separation to obtain chloroethyl sulfoxide shown in formula (I).
The reaction formula is as follows:
in the structural formulas I and II, R is selected from aryl and heteroaryl.
The anode and the cathode are respectively selected from one of a platinum electrode, a nickel electrode, a graphite electrode, a glassy carbon electrode and an RVC electrode.
The electrolyte is one or more of lithium perchlorate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium iodide, tetrabutylammonium bromide, tetrabutylammonium fluoride and the like; the amount of the electrolyte is 50 to 400 mol%, more preferably 80 to 200 mol%, based on the thiophenols.
The solvent is 1, 2-dichloroethane or a mixed solvent of the dichloroethane and water, dichloromethane, acetonitrile, tetrahydrofuran and the like.
The gas atmosphere is oxygen, air, nitrogen and argon.
The current is constant current, 5-100 mA, preferably 10-60 mA.
The reaction temperature of the preparation method is 10-80 ℃, and preferably 30-70 ℃.
The reaction time of the preparation method is 1-24 hours, and more preferably 3-12 hours.
The concentration of the substrate in the preparation method is 0.05-1 mol/L, and more preferably 0.1-0.5 mol/L.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method disclosed by the invention does not need to use metal catalysis, an oxidant and an additive, but uses green energy for electrocatalytic oxidation, the reaction is completed in one step, the distribution is not needed, the preparation method is more green and environment-friendly, the raw materials are easy to obtain, the operation is simple, the reaction chemical selectivity is high, the environment is friendly, and the like, and the preparation method has the characteristics of higher implementation value and social and economic benefits.
Detailed Description
The invention is further described below with reference to specific examples, but is not limited to the embodiments described by the specific examples listed herein.
Example 1: preparation of (2-chloroethyl) sulfinyl benzene (Ia)
Thiophenol (550mg, 5mmol)1, 2-dichloroethane (15mL), tetrabutylammonium tetrafluoroborate (1.280g,4.0mmol) were added to the reaction apparatus, and a platinum-platinum electrode was inserted, the current was adjusted to a constant current of 40mA, the reaction was stirred at 60 ℃ for 12 hours, and separation was performed by silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1, volume ratio) to obtain 582mg of (2-chloroethyl) sulfinylbenzene (Ia) as a pale yellow oily liquid, in yield: 62%, Ia formula:
1H NMR(400MHz,CDCl3)7.61(dd,J1＝8.0Hz,J2＝2.4Hz,2H),7.55-7.47(m,3H),3.97-3.90(m,1H),3.66-3.60(m,1H),3.16-3.12(m,2H)；13C NMR(400MHz,CDCl3)142.8,131.4,129.5,123.9,59.3,36.7.
MS:(EI；70eV)m/z(％)＝188(M+).
example 2: preparation of (2-chloroethyl) sulfinyl benzene (Ia)
Thiophenol (550mg, 5mmol), 1, 2-dichloroethane (15mL), tetrabutylammonium hexafluorophosphate (1.520g,4.0mmol) were charged into a reaction apparatus, and a platinum-platinum electrode was inserted, the current was adjusted to a constant current of 40mA, the reaction was stirred at 60 ℃ for 15 hours, and separation by silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1, volume ratio) gave 556mg of (2-chloroethyl) sulfinyl benzene (Ia) as a pale yellow oily liquid, in yield: 57 percent.
Example 3: preparation of (2-chloroethyl) sulfinyl benzene (Ia)
Thiophenol (550mg, 5mmol), 1, 2-dichloroethane (15mL), tetrabutylammonium iodide (1.855g,5.0mmol) were added to the reaction apparatus, and a platinum-platinum electrode was inserted, the current was adjusted to a constant current of 40mA, the reaction was stirred at 60 ℃ for 10 hours, and separation by silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1, volume ratio) gave 531mg of (2-chloroethyl) sulfinylbenzene (Ia) as a pale yellow oily liquid, in yield: 56 percent.
Example 4: preparation of (2-chloroethyl) sulfinyl benzene (Ia)
Thiophenol (110mg, 1mmol), 1, 2-dichloroethane (10mL), tetrabutylammonium tetrafluoroborate (0.640g,2.0mmol) were added to the reaction apparatus, and a platinum-carbon electrode was inserted, the current was adjusted to a constant current of 10mA, the reaction was stirred at 60 ℃ for 10 hours, and the reaction was separated by silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1, volume ratio) to obtain 132mg of (2-chloroethyl) sulfinylbenzene (Ia) as a pale yellow oily liquid, yield: 70 percent.
Example 5: preparation of (2-chloroethyl) sulfinyl benzene (Ia)
Thiophenol (110mg, 1mmol), 1, 2-dichloroethane (10mL), tetrabutylammonium tetrafluoroborate (0.640g,2.0mmol) were charged into a reaction apparatus, and a platinum-RVC electrode was inserted, the current was adjusted to a constant current of 20mA, the reaction was stirred at 60 ℃ for 5 hours, and separation by silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1 by volume) gave 165mg of (2-chloroethyl) sulfinylbenzene (Ia) as a pale yellow oily liquid, in yield: 87 percent.
Example 6: preparation of (2-chloroethyl) sulfinyl benzene (Ia)
Thiophenol (110mg, 1mmol), 1, 2-dichloroethane (10mL), tetrabutylammonium tetrafluoroborate (0.640g,2.0mmol) were charged into a reaction apparatus, and a platinum-RVC electrode was inserted, the current was adjusted to a constant current of 40mA, the reaction was stirred at 60 ℃ for 3 hours, and separation by silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1, volume ratio) gave 171mg of (2-chloroethyl) sulfinylbenzene (Ia) as a pale yellow oily liquid, in yield: 89 percent.
Example 7: preparation of (2-chloroethyl) sulfinyl benzene (Ia)
Thiophenol (550mg, 5mmol), 1, 2-dichloroethane (15mL), tetrabutylammonium tetrafluoroborate (1.600g,5.0mmol) were charged into a reaction apparatus, and a platinum-RVC electrode was inserted, the current was adjusted to a constant current of 60mA, the reaction was stirred at 60 ℃ for 20 hours, and separation by silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1, volume ratio) gave 687mg of (2-chloroethyl) sulfinylbenzene (Ia) as a pale yellow oily liquid, in yield: 72 percent.
Example 8: preparation of (2-chloroethyl) sulfinyl benzene (Ia)
Thiophenol (550mg, 5mmol), 1, 2-dichloroethane (30mL), tetrabutylammonium tetrafluoroborate (3.200g,10.0mmol) were charged into a reaction apparatus, and a platinum-RVC electrode was inserted, the current was adjusted to a constant current of 40mA, the reaction was stirred at 60 ℃ for 12 hours, and separation by silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1, volume ratio) gave 708mg of (2-chloroethyl) sulfinylbenzene (Ia) as a pale yellow oily liquid, in yield: 75 percent.
Example 9: preparation of (2-chloroethyl) sulfinyl benzene (Ia)
Thiophenol (550mg, 5mmol), 1, 2-dichloroethane (20mL), water (1mL), tetrabutylammonium tetrafluoroborate (1.650g,5.0mmol) were charged into the reaction apparatus, and a platinum-RVC electrode was inserted, the current was adjusted to a constant current of 40mA, the reaction was stirred at 60 ℃ for 12 hours, and the reaction mixture was chromatographed on a silica gel column (eluent n-hexane: ethyl acetate 4:1, volume ratio) to obtain 832mg of (2-chloroethyl) sulfinylbenzene (Ia) as a pale yellow oily liquid, yield: 88 percent.
Example 10: preparation of (2-chloroethyl) sulfinyl benzene (Ia)
Thiophenol (550mg, 5mmol), 1, 2-dichloroethane (10mL), acetonitrile (10mL), tetrabutylammonium tetrafluoroborate (1.650g,5.0mmol) were charged into the reaction apparatus, and a platinum-RVC electrode was inserted, the current was adjusted to a constant current of 40mA, the reaction was stirred at 60 ℃ for 12 hours, and the reaction mixture was chromatographed on a silica gel column (eluent n-hexane: ethyl acetate 4:1, volume ratio) to obtain 613mg of (2-chloroethyl) sulfinylbenzene (Ia) as a pale yellow oily liquid, yield: 65 percent.
Example 11: preparation of (2-chloroethyl) sulfinyl benzene (Ia)
Thiophenol (550mg, 5mmol), 1, 2-dichloroethane (20mL), tetrabutylammonium tetrafluoroborate (1.650g,5.0mmol) were charged into a reaction apparatus, and a platinum-RVC electrode was inserted, the current was adjusted to a constant current of 40mA, and the reaction was stirred at 40 ℃ for 12 hours, and subjected to silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1, volume ratio) to obtain 630mg of (2-chloroethyl) sulfinylbenzene (Ia) as a pale yellow oily liquid, yield: 67%.
Example 12: preparation of (2-chloroethyl) sulfinyl benzene (Ia)
Thiophenol (550mg, 5mmol), 1, 2-dichloroethane (20mL), tetrabutylammonium tetrafluoroborate (1.650g,5.0mmol) were charged into a reaction apparatus, and a platinum-RVC electrode was inserted, the current was adjusted to a constant current of 40mA, the reaction was stirred at 60 ℃ for 12 hours, and separation by silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1, volume ratio) gave 796mg of (2-chloroethyl) sulfinylbenzene (Ia) as a pale yellow oily liquid, in yield: 84 percent.
Example 13: preparation of (2-chloroethyl) sulfinyl benzene (Ia)
Thiophenol (550mg, 5mmol), 1, 2-dichloroethane (20mL), tetrabutylammonium tetrafluoroborate (1.650g,5.0mmol) were added to the reaction apparatus, and a platinum-RVC electrode was inserted, the current was adjusted to a constant current of 40mA, the reaction was stirred at 80 ℃ for 8 hours, and separation by silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1, volume ratio) gave 731mg of (2-chloroethyl) sulfinylbenzene (Ia) as a pale yellow oily liquid, in yield: 77 percent.
Example 14: preparation of (2-chloroethyl) sulfinyl benzene (Ia)
Thiophenol (550mg, 5mmol), 1, 2-dichloroethane (20mL), tetrabutylammonium tetrafluoroborate (1.650g,5.0mmol) were added to a reaction apparatus, and a platinum-RVC electrode was inserted, the current was adjusted to a constant current of 40mA, the reaction was stirred at 60 ℃ for 12 hours under a pure oxygen atmosphere, and separation was performed by silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1, volume ratio) to obtain 712mg of (2-chloroethyl) sulfinylbenzene (Ia) as a pale yellow oily liquid, yield: 75 percent.
Example 15: preparation of (2-chloroethyl) sulfinyl benzene (Ia)
Thiophenol (550mg, 5mmol), 1, 2-dichloroethane (20mL), tetrabutylammonium tetrafluoroborate (1.650g,5.0mmol) were added to a reaction apparatus, and a platinum-RVC electrode was inserted, the current was adjusted to a constant current of 40mA, and the reaction was stirred at 60 ℃ for 12 hours under an argon atmosphere, and subjected to silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1, volume ratio) to obtain (2-chloroethyl) sulfinylbenzene (Ia)681mg as a pale yellow oily liquid, yield: 72 percent.
Example 16: preparation of (2-chloroethyl) sulfinyl benzene (Ia)
Thiophenol (1.100g, 10.0mmol), 1, 2-dichloroethane (30mL), water (1.5mL), tetrabutylammonium tetrafluoroborate (3.20g,10.0mmol) were charged into a reaction apparatus, and a platinum-RVC electrode was inserted, the reaction was stirred at 60 ℃ for 24 hours under an atmosphere of nitrogen with a constant current of 50mA, and subjected to silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1 in volume ratio) to obtain 1.670g of (2-chloroethyl) sulfinyl benzene (Ia) as a pale yellow oily liquid, yield: 88 percent.
Example 17: preparation of 4-methyl-1- (2-chloroethyl) sulfinyl benzene (Ib)
4-methylphenylthiophenol (620mg, 5.0mmol), 1, 2-dichloroethane (20mL), water (1.0mL), tetrabutylammonium tetrafluoroborate (1.650g,5.0mmol) were charged into a reaction apparatus with a platinum-RVC electrode interposed, and the reaction was stirred at 60 ℃ for 12 hours with a constant current of 40mA, and separated by silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1 by volume) to obtain 566mg of 4-methyl-1- (2-chloroethyl) sulfinyl benzene (Ib) as a pale yellow oily liquid, yield: 56 percent, and the Ib structural formula is as follows:
1H NMR(400MHz,CDCl3)7.51(d,J＝8.0Hz,2H),7.33(d,J＝8.0Hz,2H),3.97-3.90(m,1H),3.66-3.60(m,1H),3.13(t,J＝7.2Hz,2H),2.41(s,3H)；13C NMR(100MHz,CDCl3)142.0,139.4,130.2,130.0,59.3,36.8,21.4.
example 18: preparation of 2, 4-methyl-1- (2-chloroethyl) sulfinyl benzene (Ic)
2, 4-Methylphenylphenol (690mg, 5.0mmol), 1, 2-dichloroethane (20mL), water (1.0mL), tetrabutylammonium tetrafluoroborate (1.650g,5.0mmol) were charged into a reaction apparatus, and a platinum-RVC electrode was inserted, the reaction was stirred at 60 ℃ for 14 hours with a constant current of 40mA, and subjected to silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1, volume ratio) to give 2, 4-methyl-1- (2-chloroethyl) sulfinyl benzene (Ic)581mg as a pale yellow oily liquid, yield: 54%, Ic formula is:
1H NMR(400MHz,CDCl3)7.75(d,J＝8.0Hz,1H),7.23(d,J＝8.0Hz,1H),7.0(s,1H),4.02-3.71(m,1H),3.71-3.67(m,1H),3.18-3.11(m,1H),3.06-3.00(m,1H),2.36(s,1H),2.34(s,1H)；13C NMR(100MHz,CDCl3)141.6,137.7,134.3,131.7,128.1,123.8,57.8,37.1,21.2,18.0.
example 19: preparation of 2-methoxy-1- (2-chloroethyl) sulfinyl benzene (Id)
2-Methoxythiophenol (700mg, 5.0mmol), 1, 2-dichloroethane (20mL), water (1.0mL), tetrabutylammonium tetrafluoroborate (1.650g,5.0mmol) were charged into a reaction apparatus, and a platinum-RVC electrode was inserted, the reaction was stirred at 60 ℃ for 24 hours with a constant current of 40mA, and separated by silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1, volume ratio) to obtain 578mg of 2-methoxy-1- (2-chloroethyl) sulfinylbenzene (Id) as a pale yellow oily liquid, with yield: 53% and Id of the formula:
1H NMR(400MHz,CDCl3)7.74(dd,J1＝7.6Hz,J2＝1.6Hz,1H),7.45(td,J1＝8.0Hz,J2＝2.0Hz,1H),7.17(t,J＝7.6Hz,1H),6.92(d,J＝8.0Hz,1H),3.99-3.92(m,1H),3.88(s,3H),3.65-3.59(m,1H),3.47-3.40(m,1H),3.16-3.09(m,1H)；13C NMR(100MHz,CDCl3)155.0,132.4,129.7,125.3,121.7,110.8,55.8,54.9,36.7.
example 20: preparation of 4-fluoro-1- (2-chloroethyl) sulfinyl benzene (Ie)
4-fluorobenzothiophenol (640mg, 5.0mmol), 1, 2-dichloroethane (20mL), water (1.0mL), tetrabutylammonium tetrafluoroborate (1.650g,5.0mmol) were charged into a reaction apparatus, and a platinum-RVC electrode was inserted, the reaction was stirred at 60 ℃ for 12 hours with a constant current of 40mA, and after separation by silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1 by volume), 824mg of 4-fluoro-1- (2-chloroethyl) sulfinyl benzene (Ie) was obtained as a colorless liquid in yield: 80%, and the structural formula of Ie is:
1H NMR(400MHz,CDCl3)7.63-7.60(m,2H),7.23-7.19(m,2H),3.95-3.88(m,1H),366-3.60(m,1H),3.13-3.10(m,2H)；13C NMR(100MHz,CDCl3)165.8,163.3,138.2(d,JC-F＝130.0Hz),136.3(d,JC-F＝292.0Hz),116.9(d,3JC-F＝225Hz),59.6,36.6.
example 21: preparation of 4-chloro-1- (2-chloroethyl) sulfinyl benzene (If)
4-chlorothiophenol (720mg, 5.0mmol), 1, 2-dichloroethane (20mL), water (1.0mL), tetrabutylammonium tetrafluoroborate (1.650g,5.0mmol) were charged into the reaction apparatus with the interposition of a platinum-RVC electrode, and the reaction was stirred at 60 ℃ for 12 hours with constant current of 40mA, and separated by silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1, volume ratio) to obtain 812mg of 4-chloro-1- (2-chloroethyl) sulfinyl benzene (If) as a white solid in yield: 73%, and If has the structural formula:
1H NMR(400MHz,CDCl3)7.58(dd,J1＝8.4Hz,J2＝1.2Hz,2H),7.52(dd,J1＝8.4Hz,J2＝1.6Hz,2H),3.99-3.69(m,1H),3.66(q,J＝5.6Hz,1H),3.20-3.09(m,2H)；13C NMR(100MHz,CDCl3)141.4,137.7,129.8,125.4,59.5,36.5.
example 22: preparation of 2- (2-chloroethyl) sulfinyl naphthalene (Ig)
2-Napthalol (800.0mg, 5.0mmol), 1, 2-dichloroethane (20mL), water (1.0mL), tetrabutylammonium tetrafluoroborate (1.650g,5.0mmol) were charged into the reaction apparatus, and a platinum-RVC electrode was inserted, the reaction was stirred at 60 ℃ for 12 hours with a constant current of 40mA, and the mixture was separated by silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1, volume ratio) to obtain 722mg of 2- (2-chloroethyl) sulfinylnaphthalene (Ig) as a white solid, yield: 60%, Ig structural formula is:
1H NMR(400MHz,CDCl3)8.21(s,1H),8.01(d,J＝8.4Hz),7.96-7.91(m,2H),7.63-7.59(m,3H),4.04-3.97(m,1H),3.70-3.64(m,1H),3.31-3.19(m,2H)；13C NMR(100MHz,CDCl3)139.8,134.6,132.9,129.8,128.5,128.1,128.0,127.6,124.8,119.6,59.1.
example 23: preparation of 2- (2-chloroethyl) sulfinyl thiophene (Ih)
2-thiothiothiophene (580.0mg, 5.0mmol), 1, 2-dichloroethane (20mL), water (1.0mL), tetrabutylammonium tetrafluoroborate (1.650g,5.0mmol) were charged into a reaction apparatus, and a platinum-RVC electrode was inserted, the reaction was stirred at 60 ℃ for 12 hours with a constant current of 40mA, and the mixture was separated by silica gel column chromatography (eluent n-hexane: ethyl acetate 4:1 by volume) to obtain 407mg of 2- (2-chloroethyl) sulfinyl thiophene (Ih) as a brown liquid, yield: 42%, and Ih has the formula:
1H NMR(400MHz,CDCl3)7.70(dd,J1＝5.2Hz,J2＝1.2Hz,1H),7.53(dd,J1＝3.6Hz,J2＝1.2Hz,1H),7.15(dd,J1＝5.2Hz,J2＝3.6Hz,1H),3.99-3.93(m,1H),3.77-3.71(m,1H),3.54-3.48(m,1H),3.32-3.25(m,1H)；13C NMR(100MHz,CDCl3)144.6,131.7,130.3,127.7,60.5,36.9.
the foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and enhancements can be made without departing from the spirit of the present invention, and these modifications and enhancements should also be considered within the scope of the present invention.
Claims (8)
1. An electrochemical synthesis method of chloroethyl sulfoxide compounds is characterized in that the reaction is carried out in an undissociated electrolytic tank, aryl thiophenol compounds shown in formula (II), 1, 2-dichloroethane and electrolyte are dissolved in a solvent to obtain a reaction solution, the reaction solution is added into the electrolytic tank, an electrode is inserted into the reaction solution, constant current is conducted in a proper gas atmosphere for stirring reaction, and after the reaction is finished, column chromatography separation is carried out to obtain chloroethyl sulfoxide shown in formula (I); the reaction formula is as follows:
wherein R is selected from aryl and heteroaryl;
the solvent is a mixed solvent of 1, 2-dichloroethane and water;
the constant current is 5-100 mA, the reaction temperature is 10-80 ℃, and the reaction time is 1-24 hours;
the electrolyte is one or more of lithium perchlorate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium iodide, tetrabutylammonium bromide and tetrabutylammonium fluoride; wherein the dosage of the electrolyte is 50-400 mol% of the aryl thiophenol compound;
the suitable gas atmosphere is oxygen, air, nitrogen, argon.
2. The method for electrochemically synthesizing a chloroethyl sulfoxide compound according to claim 1, wherein the positive electrode and the negative electrode are each selected from one of a platinum electrode, a nickel electrode, a graphite electrode, a glassy carbon electrode, and an RVC electrode.
3. The electrochemical synthesis method of chloroethyl sulfoxide compound according to claim 1, wherein the electrolyte is one or more of lithium perchlorate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium iodide, tetrabutylammonium bromide and tetrabutylammonium fluoride; wherein the dosage of the electrolyte is 80-200 mol% of the aryl thiophenol compound.
4. The electrochemical synthesis method of chloroethyl sulfoxide compounds according to claim 1, characterized in that the constant current is 10-60 mA.
5. The electrochemical synthesis method of chloroethyl sulfoxide compounds as claimed in claim 1, characterized in that the reaction temperature is 30-70 ℃.
6. The electrochemical synthesis method of chloroethyl sulfoxide compounds according to claim 1, characterized in that the reaction time is 3-12 hours.
7. The electrochemical synthesis method of chloroethyl sulfoxide compounds according to claim 1, wherein the concentration of aryl thiophenol compounds is 0.05-1 mol/L.
8. The electrochemical synthesis method of chloroethyl sulfoxide compounds according to claim 1, wherein the concentration of aryl thiophenol compounds is 0.1-0.5 mol/L.
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| EFFICIENT SYHTHESIS OF α-CHLOKOVIHYL PHEHYL SULFONE;Krzysztof Wojciechowskl;《《Organic Preparation and Procedure International》》;20090218;第20卷(第5期);第493-496页 * |
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