CN111534832A - Preparation method of sulfoxide compound under electrocatalysis - Google Patents
Preparation method of sulfoxide compound under electrocatalysis Download PDFInfo
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- CN111534832A CN111534832A CN202010516695.4A CN202010516695A CN111534832A CN 111534832 A CN111534832 A CN 111534832A CN 202010516695 A CN202010516695 A CN 202010516695A CN 111534832 A CN111534832 A CN 111534832A
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- tetrabutylammonium
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- -1 sulfoxide compound Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 16
- 239000012043 crude product Substances 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 150000003568 thioethers Chemical class 0.000 claims abstract description 6
- 238000010898 silica gel chromatography Methods 0.000 claims abstract description 3
- 238000001308 synthesis method Methods 0.000 claims abstract description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000001311 chemical methods and process Methods 0.000 claims description 2
- KVURXUSSSJWASD-UHFFFAOYSA-N fluoro(dioxido)borane tetrabutylazanium Chemical compound [O-]B([O-])F.[O-]B([O-])F.[O-]B([O-])F.[O-]B([O-])F.[O-]B([O-])F.[O-]B([O-])F.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC KVURXUSSSJWASD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 claims description 2
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 claims description 2
- QJGSRNYAKXKSDC-UHFFFAOYSA-L tetrabutylazanium;sulfite Chemical compound [O-]S([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC QJGSRNYAKXKSDC-UHFFFAOYSA-L 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 150000003462 sulfoxides Chemical class 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 6
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- GZTOWBHKEXJZAV-UHFFFAOYSA-N 1-methoxy-2-[(2-methoxyphenyl)methylsulfinylmethyl]benzene Chemical compound COC1=CC=CC=C1CS(=O)CC1=CC=CC=C1OC GZTOWBHKEXJZAV-UHFFFAOYSA-N 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000001555 benzenes Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- DUVLJBQCIZCUMW-UHFFFAOYSA-N ethylsulfinylbenzene Chemical compound CCS(=O)C1=CC=CC=C1 DUVLJBQCIZCUMW-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XOEQDKSHVMKNAO-UHFFFAOYSA-N 1-methoxy-2-[(2-methoxyphenyl)methylsulfanylmethyl]benzene Chemical compound COC1=CC=CC=C1CSCC1=CC=CC=C1OC XOEQDKSHVMKNAO-UHFFFAOYSA-N 0.000 description 1
- LSARSVVLJAOBKF-UHFFFAOYSA-N 1-methyl-4-[(4-methylphenyl)methylsulfinylmethyl]benzene Chemical compound C1=CC(C)=CC=C1CS(=O)CC1=CC=C(C)C=C1 LSARSVVLJAOBKF-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000711573 Coronaviridae Species 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 206010024229 Leprosy Diseases 0.000 description 1
- 208000007107 Stomach Ulcer Diseases 0.000 description 1
- WHCUDKRXQARACL-UHFFFAOYSA-N acetonitrile;1,2-dichloroethane Chemical compound CC#N.ClCCCl WHCUDKRXQARACL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229960000860 dapsone Drugs 0.000 description 1
- CJBJHOAVZSMMDJ-HEXNFIEUSA-N darunavir Chemical compound C([C@@H]([C@H](O)CN(CC(C)C)S(=O)(=O)C=1C=CC(N)=CC=1)NC(=O)O[C@@H]1[C@@H]2CCO[C@@H]2OC1)C1=CC=CC=C1 CJBJHOAVZSMMDJ-HEXNFIEUSA-N 0.000 description 1
- 229960005107 darunavir Drugs 0.000 description 1
- FDSGHYHRLSWSLQ-UHFFFAOYSA-N dichloromethane;propan-2-one Chemical compound ClCCl.CC(C)=O FDSGHYHRLSWSLQ-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- AEHWKBXBXYNPCX-UHFFFAOYSA-N ethylsulfanylbenzene Chemical compound CCSC1=CC=CC=C1 AEHWKBXBXYNPCX-UHFFFAOYSA-N 0.000 description 1
- 201000005917 gastric ulcer Diseases 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 1
- VHILIAIEEYLJNA-UHFFFAOYSA-N methyl p-tolyl sulfide Chemical compound CSC1=CC=C(C)C=C1 VHILIAIEEYLJNA-UHFFFAOYSA-N 0.000 description 1
- SOHCYNFHNYKSTM-UHFFFAOYSA-N methylsulfinylmethane;oxolane Chemical compound CS(C)=O.C1CCOC1 SOHCYNFHNYKSTM-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- SBQLYHNEIUGQKH-UHFFFAOYSA-N omeprazole Chemical compound N1=C2[CH]C(OC)=CC=C2N=C1S(=O)CC1=NC=C(C)C(OC)=C1C SBQLYHNEIUGQKH-UHFFFAOYSA-N 0.000 description 1
- 229960000381 omeprazole Drugs 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003285 pharmacodynamic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/14—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
Abstract
The invention discloses a preparation method of a sulfoxide compound under electrocatalysis, belonging to the technical field of organic synthesis. The method comprises the following steps: adding a thioether compound and an electrolyte in a molar ratio of 1:0.3 into a reactor, adding a solvent, and promoting the reaction by an electrocatalytic method. After the reaction is finished, concentrating by using a rotary evaporator to obtain a crude product, and separating by using silica gel column chromatography to obtain a target product. The synthetic method is green and environment-friendly, and does not need a catalyst; the substrate can react under weak current; simple synthesis method, rapid reaction and the like. The reaction equation is as follows:
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of a sulfoxide compound under electrocatalysis.
Background
Organic sulfides are frequently present in biologically and pharmaceutically active compounds. Among them, sulfoxide is widely used as a very important organic synthesis intermediate in pharmaceuticals, natural products, and organic materials. The structure of the sulfoxide compound is modified to improve the pharmacodynamic activity of the sulfoxide compound, such as darunavir for treating novel coronavirus, omeprazole for resisting digestive tract gastric ulcer, dapsone for treating leprosy, etc. Therefore, the development of a method for efficiently and quickly synthesizing sulfoxide has important significance and is a more hot research field.
Direct oxidation of thioethers is the simplest and most efficient method for preparing sulfoxides. Most of the reported thioether oxidation systems have the defects of harsh oxidation conditions, poor reaction selectivity, difficult preparation of catalysts and the like. Particularly, the use of a large amount of transition metal catalysts such as platinum, copper, gold, etc. causes serious environmental problems.
Disclosure of Invention
In order to overcome the defects of the prior art for synthesizing the sulfoxide compound, the invention provides a method for preparing the sulfoxide compound under the electrocatalytic promotion.
Electrocatalysis is a sustainable, green process. Electrocatalysis takes electrons as a reaction reagent, so that toxic or difficultly-treated catalysts can be avoided, reaction products are high in purity and easy to separate, and the environment is hardly polluted; in the electrocatalytic reaction, the electrode voltage or current can be changed to regulate and control the reaction rate so as to avoid side reaction, thereby improving the selectivity and yield of the target product.
A method for preparing a sulfoxide compound by an electrocatalytic process, the sulfoxide compound having a structure represented by formula I:
wherein R is1Is a benzene ring, a substituted benzene ring, or an alkyl group; r2Is a benzene ring, a substituted benzene ring, or an alkyl group. The method is characterized in that a thioether compound and an electrolyte in a molar ratio of 1:0.3 are added into a reactor, a solvent is added, and the reaction is promoted by an electrocatalysis method. After the reaction is finished, concentrating by using a rotary evaporator to obtain a crude product, and separating by using silica gel column chromatography to obtain a target product.
The chemical process is shown in a reaction formula II:
in the synthesis of the sulfoxide compound (I) of the invention, the current is 4mA, the temperature is 25 ℃, and the time is 7 h.
In the synthesis of the sulfoxide compound (I) of the present invention, the oxygen is derived from air.
In the synthesis of the sulfoxide compound (I) of the present invention, the oxidation reaction in the method is carried out in an organic solvent, and the solvent includes any one of methanol, DMSO, acetonitrile, acetone, tetrahydrofuran, dichloromethane, and 1, 2-dichloroethane. Preferably, the reaction solvent is 1, 2-dichloroethane.
In the synthesis of the sulfoxide compound (I), the electrolyte includes one of tetrabutylammonium tetrafluoroborate, tetrabutylammonium perchlorate, tetrabutylammonium hexafluoroborate, tetrabutylammonium sulfite and tetrabutylammonium acetate. Preferably, the electrolyte is tetrabutylammonium tetrafluoroborate.
The invention has the beneficial effects that: the invention provides a new way for synthesizing sulfoxide compounds; the raw materials used by the synthetic method are simple and easily available, and the source is wide; the sulfoxide compound obtained by the method is characterized in that: the synthetic route is green and environment-friendly, and a catalyst is not needed; the reaction solvent is 1, 2-dichloroethane, and replaces a toxic solvent; the substrate can react under weak current; the synthesis method is simple and the reaction is rapid; the yield of the target compound is high, and the product is easy to purify.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
EXAMPLE 1 Synthesis of Diphenyl sulfoxide by electrocatalytic oxidation
Diphenyl sulfide (0.5mmol), tetrabutylammonium tetrafluoroborate (0.15mmol) and 1, 2-dichloroethane (8mL) were sequentially added to a 20mL electrolytic cell, a graphite electrode was used as an anode, and a platinum sheet electrode was used as a cathode. The electrolysis was carried out at 25 ℃ under a constant current of 4mA, and the reaction was carried out for 7 hours. After the reaction is finished, the solvent is removed by using a rotary evaporator to obtain a crude product, the crude product is separated by column chromatography (200-mesh silica gel with 300 meshes, petroleum ether and ethyl acetate are 5:1), and the solvent is removed by using the rotary evaporator to obtain the target product, namely the diphenyl sulfoxide 2a, wherein the yield is 97.5%.1H NMR(400MHz, CDCl3)7.65(ddd,J＝6.5,4.4,2.7Hz,4H),7.47–7.43(m,6H).
EXAMPLE 2 Synthesis of 2-methoxybenzyl sulphoxide by electrocatalytic oxidation
2-methoxybenzyl sulfide (0.5mmol), tetrabutylammonium tetrafluoroborate (0.15mmol) and 1, 2-dichloroethane (8mL) were sequentially added to a 20mL electrolytic cell, a graphite electrode was used as an anode, and a platinum sheet electrode was used as a cathode. The electrolysis was carried out at 25 ℃ under a constant current of 4mA, and the reaction was carried out for 7 hours. After the reaction is finished, the solvent is removed by using a rotary evaporator to obtain a crude product, the crude product is separated by column chromatography (200-mesh silica gel with 300 meshes, petroleum ether and ethyl acetate are 1:1), and the solvent is removed by using the rotary evaporator to obtain the target product 2-methoxybenzyl sulfoxide 2b, wherein the yield is 91%.
EXAMPLE 3 Synthesis of 4-methylbenzyl sulfoxide by electrocatalytic oxidation
4-methyl phenyl methyl sulfide (0.5mmol), tetrabutylammonium tetrafluoroborate (0.15mmol) and 1, 2-dichloroethane (8mL) are sequentially added into a 20mL electrolytic cup, a graphite electrode is adopted as an anode, and a platinum sheet electrode is adopted as a cathode. The electrolysis was carried out at 25 ℃ under a constant current of 4mA, and the reaction was carried out for 7 hours. After the reaction is finished, the solvent is removed by using a rotary evaporator to obtain a crude product, the crude product is separated by column chromatography (200-mesh silica gel with 300 meshes, petroleum ether and ethyl acetate are 1:1), and the solvent is removed by using the rotary evaporator to obtain the target product 2-methoxybenzyl sulfoxide 3b, wherein the yield is 71%.
EXAMPLE 4 Synthesis of Ethyl phenyl sulfoxide by electrocatalytic oxidation
Ethyl phenyl sulfide (0.5mmol), tetrabutylammonium tetrafluoroborate (0.15mmol) and 1, 2-dichloroethane (8mL) were added in this order to a 20mL electrolytic cell, using a graphite electrode as the anode and a platinum sheet electrode as the cathode. The electrolysis was carried out at 25 ℃ under a constant current of 4mA, and the reaction was carried out for 7 hours. After the reaction is finished, the solvent is removed by using a rotary evaporator to obtain a crude product, the crude product is separated by column chromatography (200-mesh silica gel of 300 meshes, petroleum ether and ethyl acetate are 1:1), and the solvent is removed by using the rotary evaporator to obtain the target product ethyl phenyl sulfoxide 4b, wherein the yield is 83.1%.
EXAMPLE 5 Synthesis of 4-Fluorothiobenzylsulfoxide by electrocatalytic oxidation
4-Fluorothiobenzylsulfide (0.5mmol), tetrabutylammonium tetrafluoroborate (0.15mmol) and 1, 2-dichloroethane (8mL) are sequentially added into a 20mL electrolytic cup, a graphite electrode is adopted as an anode, and a platinum sheet electrode is adopted as a cathode. The electrolysis was carried out at 25 ℃ under a constant current of 4mA, and the reaction was carried out for 7 hours. After the reaction is finished, the solvent is removed by using a rotary evaporator to obtain a crude product, the crude product is separated by column chromatography (200-mesh silica gel with 300 meshes, petroleum ether and ethyl acetate are 1:1), and the solvent is removed by using the rotary evaporator to obtain the target product 4-fluorothiobenzyl sulfoxide 5b, wherein the yield is 78.3%.
Example 6 examination of solvent
Referring to example 1, sulfoxide products were prepared with varying solvent selection (as shown in table 1) and other conditions. The yields of the obtained products are shown in table 1.
TABLE 1 preparation of sulfoxide products in different solvents
| Kind of solvent | DCE | MeCN | MeOH | CH3COCH3 | CH2Cl2 | THF | DMSO |
| Yield (%) | 97.5 | 38 | 36 | 49.2 | 20 | 75.2 | 21.4 |
Example 7 examination of electrolyte
Referring to example 1, sulfoxide products were prepared with changing electrolytes and other conditions, and the yields of the obtained products are shown in Table 2
TABLE 2 preparation of sulfoxide products from different electrolytes
| Kind of electrolyte | nBu4NClO4 | nBu4NPF6 | nBu4NHSO4 | nBu4NOAc |
| Yield (%) | 66.1 | 82.5 | 89.5 | 79.2 |
Claims (5)
1. A method for preparing a sulfoxide compound under electrocatalysis, wherein the sulfoxide compound has a structure shown as a formula I:
wherein R is1Is a benzene ring, a substituted benzene ring, or an alkyl group; r2Is a benzene ring, a substituted benzene ring, or an alkyl group. The method is characterized in that a thioether compound and an electrolyte in a molar ratio of 1:0.3 are added into a reactor, a solvent is added, and the reaction is promoted by an electrocatalysis method. After the reaction is finished, concentrating by using a rotary evaporator to obtain a crude product, and separating by using silica gel column chromatography to obtain a target product. The chemical process is shown in a reaction formula II:
2. the synthesis method according to claim 1, characterized in that the reaction current is 4mA, the reaction temperature is 25 ℃ and the reaction time is 7 h.
3. The method of synthesis of claim 1, wherein the oxygen is derived from air.
4. The method according to claim 1, wherein the reaction solvent is selected from the group consisting of methanol, DMSO, acetonitrile, acetone, tetrahydrofuran, dichloromethane, and 1, 2-dichloroethane.
5. The method of claim 1, wherein the electrolyte comprises one of tetrabutylammonium tetrafluoroborate, tetrabutylammonium perchlorate, tetrabutylammonium hexafluoroborate, tetrabutylammonium sulfite, tetrabutylammonium acetate.
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| CN202010516695.4A CN111534832A (en) | 2020-06-08 | 2020-06-08 | Preparation method of sulfoxide compound under electrocatalysis |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608257A (en) * | 2020-12-24 | 2021-04-06 | 新疆大学 | Synthesis method of sulfoxide compound |
| CN113402434A (en) * | 2021-06-17 | 2021-09-17 | 常州工程职业技术学院 | Novel NH-sulfoxide imine compound and synthetic method thereof |
| CN113737206A (en) * | 2021-09-16 | 2021-12-03 | 青岛科技大学 | Synthesis method for preparing sulfoxide compound from thioether under electrochemistry |
| CN114250483A (en) * | 2021-12-31 | 2022-03-29 | 宁波南大光电材料有限公司 | Synthesis method for preparing compound containing diphenyl sulfoxide by electrochemical catalytic oxidation |
-
2020
- 2020-06-08 CN CN202010516695.4A patent/CN111534832A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608257A (en) * | 2020-12-24 | 2021-04-06 | 新疆大学 | Synthesis method of sulfoxide compound |
| CN113402434A (en) * | 2021-06-17 | 2021-09-17 | 常州工程职业技术学院 | Novel NH-sulfoxide imine compound and synthetic method thereof |
| CN113737206A (en) * | 2021-09-16 | 2021-12-03 | 青岛科技大学 | Synthesis method for preparing sulfoxide compound from thioether under electrochemistry |
| CN114250483A (en) * | 2021-12-31 | 2022-03-29 | 宁波南大光电材料有限公司 | Synthesis method for preparing compound containing diphenyl sulfoxide by electrochemical catalytic oxidation |
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