CN110256307B - Method for synthesizing sulfoxide compound - Google Patents
Method for synthesizing sulfoxide compound Download PDFInfo
- Publication number
- CN110256307B CN110256307B CN201910565960.5A CN201910565960A CN110256307B CN 110256307 B CN110256307 B CN 110256307B CN 201910565960 A CN201910565960 A CN 201910565960A CN 110256307 B CN110256307 B CN 110256307B
- Authority
- CN
- China
- Prior art keywords
- reaction
- compound
- sulfoxide
- arh
- ethyl acetate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing sulfoxide compounds, belonging to the technical field of organic compound synthesis. The method comprises the following steps: perylene bisimide is used as a catalyst, and under the condition of illumination, a thioether compound is catalyzed to react with an oxygen agent to obtain a sulfoxide compound. The method realizes the selective oxidation of thioether catalyzed by perylene bisimide under visible light for the first time, and successfully constructs sulfoxide suborganisms with high yield; the method has the advantages of mild reaction conditions, high reaction efficiency, wide substrate application range, high atom utilization rate, high reaction regioselectivity and chemical selectivity and potential application value.
Description
Technical Field
The invention particularly relates to a method for synthesizing sulfoxide compounds, belonging to the technical field of organic compound synthesis.
Background
Selective oxidation of organic compounds is one of the most fundamental reactions in organic synthesis and also one of the most critical challenges in industrial chemistry. Traditionally, toxic or hazardous oxidants, such as toxic metal oxides and peroxides, are commonly used in stoichiometric amounts for these chemical transformations. Due to increasing concern over environmental issues, there is a wide effort to develop cleaner synthetic strategies that utilize oxygen as the most economical and greenest end oxidant. However, due to its triplet ground state structure, oxygen is inactive and is difficult to activate, especially for inert carbon-hydrogen bonds. In order to overcome the high oxidation potential, a precious and toxic noble metal catalyst or a porous graphene/carbon nitride composite material at high temperature and high pressure is used. In addition, since photocatalysis has been recognized as a useful synthetic method and rapidly developed in numerous practical fields and basic research, a metal photocatalytic system has also been developed for the oxidation of organic compounds, but the lack of photooxidation potential and the use of noble metals severely limit its practical applications. Therefore, there is a pressing need for a selective photocatalytic oxidation metal-free photocatalyst that provides an environmentally friendly alternative synthetic route under mild conditions. However, the use of metal-free photocatalysts in selective oxidation is still relatively rare.
Selective oxidation of thioethers is an important means for functional group interconversion in organic synthesis. According to different thioether catalytic reaction systems, different products such as sulfoxide and sulfone compounds can be obtained. Among these, sulfoxides are one of the most important and valuable components of various fine chemicals and pharmaceuticals. However, many of the reactions in these systems still require harsh reaction conditions with metal-containing waste and low selectivity.
Disclosure of Invention
In order to solve the problems, the invention uses perylene bisimide as an organic photocatalyst to realize the selective oxidation of thioether into sulfoxide under visible light. And the selective oxidation of thioether into sulfoxide is realized by optimizing the reaction conditions such as catalyst, dosage, solvent and the like.
The photocatalytic reaction induced by visible light is widely applied to modern organic synthesis and pharmaceutical synthesis due to the characteristics of greenness, high efficiency and sustainability. The catalytic strategy can generate various active substances under mild reaction, and realize the formation of various intermediates and the construction of various chemical bonds. The perylene bisimide compound has a larger rigid coplanar structure and a conjugated system, has the advantages of better photochemical stability and thermal stability, larger Stokes shift, higher fluorescence quantum yield, easy-to-modify structural characteristics and the like, and is widely applied to the fields of traditional dyes, organic photoelectric materials, fluorescent probes and the like. The invention realizes a series of photocatalytic reactions by using the perylene bisimide as the organic photocatalyst, expands the application range of the perylene bisimide as the organic photocatalyst and lays a foundation for subsequent research.
The first purpose of the invention is to provide a method for synthesizing sulfoxide compounds, which comprises the step of reacting a thioether compound with an oxidant under the illumination of visible light in an organic solvent by using a perylene bisimide (PDI) as a photocatalyst to obtain the sulfoxide compounds.
In one embodiment of the present invention, the reaction equation of the method is as follows:
wherein R1 and R2 in the thioether compound are respectively and independently selected from any one of methyl, deuterated methyl, unsubstituted or halogen-substituted C1-C6 straight-chain or branched-chain alkyl, unsubstituted or halogen-substituted C3-C10 cycloalkyl, unsubstituted or substituted C3-C5 aromatic ring and aromatic heterocycle; wherein halogen represents fluorine, chlorine, bromine or iodine.
In one embodiment of the present invention, R is1Or R2Any of the following is preferred: from halogen, -NO2、-OMe、-Me、-tBu substituted or unsubstituted benzene, toluene, methyl, ethyl, propenyl, butyl.
In one embodiment of the present invention, the perylene imide compound has the following structural formula:
in one embodiment of the invention, the molar equivalent of the photocatalyst perylene imide compound relative to the thioether compound is not less than 5 mol%.
In one embodiment of the present invention, the organic solvent includes one or more of an alcohol solvent, a halogenated hydrocarbon, an aromatic hydrocarbon, dimethyl sulfone, an ester, a heterocyclic aromatic hydrocarbon, an aliphatic hydrocarbon, an amide solvent, and acetonitrile.
In one embodiment of the invention, the light source of the visible light is a 5-50W light emitting diode light source, wherein the color of the light source includes, but is not limited to, red, green, blue, cyan, yellow, white, amber.
In one embodiment of the invention, the reaction is carried out at room temperature for 8-20 h.
In one embodiment of the invention, the method further comprises: after the reaction is finished, adding water and an organic solvent which cannot be mutually dissolved with the water into the reaction solution, separating the solution, further extracting the obtained water layer by using the organic solvent, combining the organic layers, removing the organic solvent in the organic layers to obtain a crude product, and purifying the crude product by using a chromatographic column.
In one embodiment of the present invention, the extraction is based on the solubility of the product and non-product in different solvents, and the preferred solvent for the product and the preferred solvent for the non-product are selected separately so that the product is transferred more to its preferred solvent.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention provides a selective oxidation method for synthesizing perylene bisimide catalyzed thioether under visible light, which uses a green, easily obtained, efficient and sustainable visible light source as reaction energy,
2) the invention provides a selective oxidation method for synthesizing thioethers catalyzed by perylene bisimide under visible light, which adopts perylene bisimide as a photocatalyst to oxidize thioethers under the condition of no metal participation, the yield of sulfoxide reaches more than 80%, the selectivity is 100%, and the method has higher universality to substrates.
3) The invention provides a selective oxidation method for synthesizing perylene bisimide catalyzed thioether under visible light, which uses oxygen as an oxidant, avoids using a strong oxidant, performs a reaction under a mild condition, and has the advantages of high reaction efficiency, wide substrate application range, high atom utilization rate, high reaction regioselectivity and chemical selectivity and potential application value.
Drawings
FIG. 1 is a hydrogen nuclear magnetic resonance spectrum of a sulfoxide derivative obtained in example 1 of the present invention.
FIG. 2 is a hydrogen nuclear magnetic resonance spectrum of a sulfoxide derivative obtained in inventive example 2.
FIG. 3 is a hydrogen nuclear magnetic resonance spectrum of a sulfoxide derivative obtained in example 3 of the present invention.
FIG. 4 is a hydrogen nuclear magnetic resonance spectrum of a sulfoxide derivative obtained in inventive example 4.
FIG. 5 is a hydrogen nuclear magnetic resonance spectrum of a sulfoxide derivative obtained in inventive example 5.
FIG. 6 is a hydrogen nuclear magnetic resonance spectrum of a sulfoxide derivative obtained in inventive example 6.
FIG. 7 is a hydrogen nuclear magnetic resonance spectrum of a sulfoxide derivative obtained in inventive example 7.
FIG. 8 is a hydrogen nuclear magnetic resonance spectrum of a sulfoxide derivative obtained in inventive example 8.
FIG. 9 is a hydrogen nuclear magnetic resonance spectrum of a sulfoxide derivative obtained in inventive example 9.
FIG. 10 is a hydrogen nuclear magnetic resonance spectrum of a sulfoxide derivative obtained in inventive example 10.
FIG. 11 is a hydrogen nuclear magnetic resonance spectrum of a sulfoxide derivative obtained in inventive example 11.
FIG. 12 is a hydrogen nuclear magnetic resonance spectrum of a sulfoxide derivative obtained in inventive example 12.
FIG. 13 is a hydrogen nuclear magnetic resonance spectrum of a sulfoxide derivative obtained in inventive example 13.
FIG. 14 is a hydrogen nuclear magnetic resonance spectrum of a sulfoxide derivative obtained in inventive example 14.
FIG. 15 is a hydrogen nuclear magnetic resonance spectrum of a sulfoxide derivative obtained in inventive example 15.
FIG. 16 is a hydrogen nuclear magnetic resonance spectrum of a sulfoxide derivative obtained in inventive example 16.
FIG. 17 is a hydrogen nuclear magnetic resonance spectrum of a sulfoxide derivative obtained in inventive example 17.
FIG. 18 is a hydrogen nuclear magnetic resonance spectrum of a sulfoxide derivative obtained in inventive example 18.
FIG. 19 is a schematic of a synthetic scheme of the present invention.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the use and purpose of these examples are merely to illustrate the present invention, and the present invention is not limited to the actual scope of the present invention in any form, and the present invention is not limited to these.
EXAMPLE 1 preparation of benzyl phenyl sulfoxide
In a dry Schlenk reaction tube, benzylphenylsulfide (0.25mmol) sulfide and PDI (0.5 mol%), a compound of formula A, were added to methanol (2.0 mL). Next, a balloon was filled with oxygen and fixed to the top of the schlenk reaction tube. The reaction was performed at room temperature under atmospheric oxygen with 15W white CFL irradiation. After the reaction was completed, brine was added to the reaction. The aqueous phase was re-extracted with ethyl acetate. Synthetic organic extracts in Na2SO4The residue was separated by silica gel column chromatography (petroleum ether: ethyl acetate: 10:1), and purified to obtain a white viscous solid (yield: 95%; selectivity: 100%).1H NMR(400MHz,CDCl3):δppm 7.47-7.36(m,5H,ArH),7.29-7.21(m,3H,ArH),6.98-6.96(m,2H,ArH),4.00-3.97(m,2H,CH2).
EXAMPLE 2 preparation of Diphenylmethyl sulfoxide
In a dry Schlenk reaction tube, diphenylmethyl sulfide (0.25mmol) sulfide and PDI (0.5 mol%) as a compound of formula B were added to methanol (2.0 mL). Next, a balloon was filled with oxygen and fixed to the top of the schlenk reaction tube. The reaction was performed at room temperature under atmospheric oxygen with 15W white CFL irradiation. After the reaction was completed, brine was added to the reaction. The aqueous phase was re-extracted with ethyl acetate. Synthetic organic extracts in Na2SO4Drying, vacuum concentrating, and performing silica gel column chromatography on the obtained residue(Petroleum ether: ethyl acetate: 10:1) and purified to give a white viscous solid (yield: 90%; selectivity: 100%).1H NMR(400MHz,CDCl3):δppm 7.40-7.34(m,3H,ArH),7.30-7.28(m,2H,ArH),3.94-3.86(m,2H,CH2).
EXAMPLE 3 preparation of Methylphenylsulfoxide
In a dry Schlenk reaction tube, methyl phenyl sulfide (0.25mmol) sulfide and PDI (0.5 mol%), a compound of formula A, were added to methanol (2.0 mL). Next, a balloon was filled with oxygen and fixed to the top of the schlenk reaction tube. The reaction was performed at room temperature under atmospheric oxygen with 15W white CFL irradiation. After the reaction was completed, brine was added to the reaction. The aqueous phase was re-extracted with ethyl acetate. Synthetic organic extracts in Na2SO4The residue was separated by silica gel column chromatography (petroleum ether: ethyl acetate: 10:1), and purified to obtain a white viscous solid (yield: 94%; selectivity: 100%).1H NMR(400MHz,CDCl3):δppm 7.67-7.64(m,2H,ArH),7.56-7.48(m,3H,ArH),2.73(s,3H,CH3).
EXAMPLE 4 preparation of p-chlorophenyl methyl sulfoxide
In a dry Schlenk reaction tube, p-chlorophenylmethylsulfide (0.25mmol) and PDI (0.5 mol%), a compound of formula A, were added to methanol (2.0 mL). Next, a balloon was filled with oxygen and fixed to the top of the schlenk reaction tube. The reaction was performed at room temperature under atmospheric oxygen with 15W white CFL irradiation. After the reaction was completed, brine was added to the reaction. The aqueous phase was re-extracted with ethyl acetate. Synthetic organic extracts in Na2SO4Drying, vacuum concentrating, and treating the residue with siliconSeparation by gel column chromatography (petroleum ether: ethyl acetate: 10:1) and purification gave a white viscous solid (yield: 90%; selectivity: 100%).1H NMR(400MHz,CDCl3):δppm 7.60(d,2H,J＝8Hz,ArH),7.51(d,2H,J＝8Hz,ArH),2.73(s,3H,CH3).
EXAMPLE 5 preparation of p-bromophenyl methyl sulfoxide
In a dry Schlenk reaction tube, p-bromophenyl methyl sulfide (0.25mmol) sulfide and PDI (0.5 mol%) as a compound of formula A were added to methanol (2.0 mL). Next, a balloon was filled with oxygen and fixed to the top of the schlenk reaction tube. The reaction was performed at room temperature under atmospheric oxygen with 15W white CFL irradiation. After the reaction was completed, brine was added to the reaction. The aqueous phase was re-extracted with ethyl acetate. Synthetic organic extracts in Na2SO4The residue was separated by silica gel column chromatography (petroleum ether: ethyl acetate: 10:1), and purified to obtain a white viscous solid (yield: 87%; selectivity: 100%).1H NMR(400MHz,CDCl3):δppm 7.67(d,2H,J＝8Ha,ArH),7.53(d,2H,J＝8Hz,ArH),2.72(s,3H,CH3).
EXAMPLE 6 preparation of p-nitrophenyl-methyl sulfoxide
In a dry Schlenk reaction tube, p-nitrophenyl-methyl sulfide (0.25mmol) sulfide and PDI (0.5 mol%), a compound of formula A, are added to methanol (2.0 mL). Next, a balloon was filled with oxygen and fixed to the top of the schlenk reaction tube. The reaction was performed at room temperature under atmospheric oxygen with 15W white CFL irradiation. After the reaction was completed, brine was added to the reaction. The aqueous phase was re-extracted with ethyl acetate. Synthetic organic extracts in Na2SO4Upper dryingThe reaction mixture was concentrated in vacuo, and the resulting residue was separated by silica gel column chromatography (petroleum ether: ethyl acetate: 10:1) and purified to give a white viscous solid (yield: 80%; selectivity: 100%).1H NMR(400MHz,CDCl3):δppm 8.40(d,2H,J＝8Hz,ArH),7.85(d,2H,J＝8Hz,ArH),2.80(s,3H,CH3).
Example 7 preparation of Diphenyl sulfoxide
In a dry Schlenk reaction tube, p-diphenylsulfide (0.25mmol) sulfide and PDI (0.5 mol%) as a compound of formula A were added to methanol (2.0 mL). Next, a balloon was filled with oxygen and fixed to the top of the schlenk reaction tube. The reaction was performed at room temperature under atmospheric oxygen with 15W white CFL irradiation. After the reaction was completed, brine was added to the reaction. The aqueous phase was re-extracted with ethyl acetate. Synthetic organic extracts in Na2SO4The residue was separated by silica gel column chromatography (petroleum ether: ethyl acetate: 10:1), and purified to obtain a white viscous solid (yield: 90%; selectivity: 100%).1H NMR(400MHz,CDCl3):δppm 7.66-7.64(m,4H,ArH),7.49-7.42(m,6H,ArH).
EXAMPLE 8 preparation of p-methoxy-p-tolyl sulfoxide
In a dry Schlenk reaction tube, p-methoxy-p-tolyl sulfide (0.25mmol) sulfide and PDI (0.5 mol%), a compound of formula A, were added to methanol (2.0 mL). Next, a balloon was filled with oxygen and fixed to the top of the schlenk reaction tube. The reaction was performed at room temperature under atmospheric oxygen with 15W white CFL irradiation. After the reaction was completed, brine was added to the reaction. The aqueous phase was re-extracted with ethyl acetate. Synthetic organic extracts in Na2SO4Drying the mixture in the drying device to obtain the finished product,the residue was separated by silica gel column chromatography (petroleum ether: ethyl acetate: 10:1) and purified to obtain a white viscous solid (yield: 87%; selectivity: 100%).1H NMR(400MHz,CDCl3):δppm 7.55(d,2H,J＝8Hz,ArH),7.49(d,2H,J＝8Hz,ArH),7.25(d,2H,J＝8Hz,ArH),6.95(d,2H,J＝8Hz,ArH),3.81(s,3H,OCH3),2.36(s,3H,CH3).
EXAMPLE 9 preparation of p-chlorophenyl-p-methylphenyl sulfoxide
In a dry Schlenk reaction tube, p-chlorophenyl-p-methylphenyl sulfide (0.25mmol) sulfide and PDI (0.5 mol%) as a compound of formula A were added to methanol (2.0 mL). Next, a balloon was filled with oxygen and fixed to the top of the schlenk reaction tube. The reaction was performed at room temperature under atmospheric oxygen with 15W white CFL irradiation. After the reaction was completed, brine was added to the reaction. The aqueous phase was re-extracted with ethyl acetate. Synthetic organic extracts in Na2SO4The residue was separated by silica gel column chromatography (petroleum ether: ethyl acetate: 10:1), and purified to obtain a white viscous solid (yield: 95%; selectivity: 100%).1H NMR(400MHz,CDCl3):δppm 7.56(d,2H,J＝8Hz,ArH),7.51(d,2H,J＝8Hz,ArH),7.42(d,2H,J＝8Hz,ArH),7.27(d,2H,J＝8Hz,ArH),2.37(s,3H,CH3).
Example 103 preparation of 5, 5-dimethylphenyl-4' -methylphenylsulfoxide
In a dry Schlenk reaction tube, 3, 5-dimethylphenyl-4' -methylphenylsulfide (0.25mmol) sulfide and PDI (0.5 mol%) as a compound of formula A were added to methanol (2.0 mL). Next, a balloon was filled with oxygen and fixed to the top of the schlenk reaction tube. Oxygen gas at normal pressureThe reaction was performed at room temperature under an atmosphere with 15W white CFL irradiation. After the reaction was completed, brine was added to the reaction. The aqueous phase was re-extracted with ethyl acetate. Synthetic organic extracts in Na2SO4The residue was separated by silica gel column chromatography (petroleum ether: ethyl acetate 10:1) and purified to obtain a white viscous solid (yield: 90%; selectivity: xx%).1H NMR(400MHz,CDCl3):δppm 7.52(d,2H,J＝8Hz,ArH),7.26-7.23(m,4H,ArH),7.03(s,1H,ArH),2.36(s,3H,CH3),2.32(s,6H,2CH3).
EXAMPLE 11 preparation of p-tert-butylphenyl-phenylsulfoxide
In a dry Schlenk reaction tube, p-tert-butylphenyl-phenylsulfide (0.25mmol) and PDI (0.5 mol%), a compound of formula A, were added to methanol (2.0 mL). Next, a balloon was filled with oxygen and fixed to the top of the schlenk reaction tube. The reaction was performed at room temperature under atmospheric oxygen with 15W white CFL irradiation. After the reaction was completed, brine was added to the reaction. The aqueous phase was re-extracted with ethyl acetate. Synthetic organic extracts in Na2SO4The residue was separated by silica gel column chromatography (petroleum ether: ethyl acetate: 10:1), and purified to obtain a white viscous solid (yield: 86%, selectivity: 100%).1H NMR(400MHz,CDCl3):δppm 7.66-7.64(m,2H,ArH),7.56(d,2H,J＝8Hz,ArH),7.48-7.41(m,5H,ArH),1.30(s,9H,3CH3).
EXAMPLE 12 preparation of two-p-bromophenyl sulfoxide
In a dry Schlenk reaction tube, di-p-bromophenyl sulfide (0.25mmol) sulfide and PDI (0.5 mol%) as a compound of formula C were added to methanol (2.0 mL). Is connected withNext, a balloon was filled with oxygen and fixed to the top of the Schlenk reaction tube. The reaction was performed at room temperature under atmospheric oxygen with 15W white CFL irradiation. After the reaction was completed, brine was added to the reaction. The aqueous phase was re-extracted with ethyl acetate. Synthetic organic extracts in Na2SO4The residue was separated by silica gel column chromatography (petroleum ether: ethyl acetate: 10:1), and purified to obtain a white viscous solid (yield: 93%; selectivity: 100%).1H NMR(400MHz,CDCl3):δppm 7.61(d,2H,J＝8Hz,ArH),7.50(d,2H,J＝8Hz,ArH).
EXAMPLE 13 preparation of p-bromophenyl-phenyl sulfoxide
In a dry Schlenk reaction tube, p-bromophenyl-phenylsulfide (0.25mmol) sulfide and PDI (0.5 mol%), a compound of formula D, were added to methanol (2.0 mL). Next, a balloon was filled with oxygen and fixed to the top of the schlenk reaction tube. The reaction was performed at room temperature under atmospheric oxygen with 15W white CFL irradiation. After the reaction was completed, brine was added to the reaction. The aqueous phase was re-extracted with ethyl acetate. Synthetic organic extracts in Na2SO4The residue was separated by silica gel column chromatography (petroleum ether: ethyl acetate: 10:1), and purified to obtain a white viscous solid (yield: 92%; selectivity: 100%).1H NMR(400MHz,CDCl3):δppm 7.64-7.62(m,2H,ArH),7.59(d,2H,J＝8Hz,ArH),7.51(d,2H,J＝8Hz,ArH),7.48-7.46(m,3H,ArH).
EXAMPLE 14 preparation of ethylphenyl sulfoxide
In a dry Schlenk reaction tube, ethyl phenyl sulfide (0.25mmol) sulfide and PDI (0.5 mol%) as a formula A were added to methanol (2.0mL)A compound (I) is provided. Next, a balloon was filled with oxygen and fixed to the top of the schlenk reaction tube. The reaction was performed at room temperature under atmospheric oxygen with 15W white CFL irradiation. After the reaction was completed, brine was added to the reaction. The aqueous phase was re-extracted with ethyl acetate. Synthetic organic extracts in Na2SO4The residue was separated by silica gel column chromatography (petroleum ether: ethyl acetate: 10:1), and purified to give a pale yellow viscous solid (yield: 80%; selectivity: 100%).1H NMR(400MHz,CDCl3):δppm 7.66–7.58(m,2H),7.57–7.47(m,3H),2.84(m,J＝46.8,13.3,7.0Hz,2H),1.20(m,J＝7.4Hz,3H).
EXAMPLE 15 preparation of allylphenyl sulfoxide
In a dry Schlenk reaction tube, allyl phenyl sulfide (0.25mmol) sulfide and PDI (0.5 mol%) as a compound of formula A were added to methanol (2.0 mL). Next, a balloon was filled with oxygen and fixed to the top of the schlenk reaction tube. The reaction was performed at room temperature under atmospheric oxygen with 15W white CFL irradiation. After the reaction was completed, brine was added to the reaction. The aqueous phase was re-extracted with ethyl acetate. Synthetic organic extracts in Na2SO4The resulting residue was separated by silica gel column chromatography (petroleum ether: ethyl acetate: 10:1), and purified to obtain a pale red liquid (yield: 82%; selectivity: 100%).1H NMR(400MHz,CDCl3):δppm 7.61(m,J＝5.1,1.8Hz,2H),7.53(d,J＝5.3Hz,1H),7.51(m,J＝1.3Hz,2H),5.77–5.52(m,1H),5.34(d,J＝10.1Hz,1H),5.20(m,J＝17.0,1.2Hz,1H),3.55(m,J＝14.9,7.5Hz,2H).
EXAMPLE 16 preparation of dibutyl sulfoxide
In a dry Schlenk reaction tube in methanolTo (2.0mL) was added dibutyl sulfide (0.25mmol) and the compound of formula A as PDI (0.5 mol%). Next, a balloon was filled with oxygen and fixed to the top of the schlenk reaction tube. The reaction was performed at room temperature under atmospheric oxygen with 15W white CFL irradiation. After the reaction was completed, brine was added to the reaction. The aqueous phase was re-extracted with ethyl acetate. Synthetic organic extracts in Na2SO4The residue was separated by silica gel column chromatography (petroleum ether: ethyl acetate: 10:1), and purified to obtain a white viscous solid (yield: 95%; selectivity: 100%).1H NMR(400MHz,CDCl3):δppm 2.74–2.54(m,4H),1.73(m,J＝8.4,7.8Hz,4H),1.46m,J＝18.6,14.1,7.0Hz,4H),0.95(m,J＝7.3Hz,6H).
EXAMPLE 17 preparation of o-methoxyphenyl-methylsulfoxide
In a dry Schlenk reaction tube, n-methoxyphenyl-methylsulfide (0.25mmol) and PDI (0.5 mol%), a compound of formula A, are added to methanol (2.0 mL). Next, a balloon was filled with oxygen and fixed to the top of the schlenk reaction tube. The reaction was performed at room temperature under atmospheric oxygen with 15W white CFL irradiation. After the reaction was completed, brine was added to the reaction. The aqueous phase was re-extracted with ethyl acetate. Synthetic organic extracts in Na2SO4The residue was separated by silica gel column chromatography (petroleum ether: ethyl acetate: 10:1), and purified to obtain a white viscous solid (yield: 86%, selectivity: 100%).1H NMR(400MHz,Chloroform-d)δ7.82(m,J＝7.7,1.3Hz,1H),7.50–7.42(m,1H),7.19(t,J＝7.6Hz,1H),6.93(d,J＝8.2Hz,1H),3.89(d,J＝1.0Hz,3H),2.78(d,J＝1.0Hz,3H).
EXAMPLE 18 preparation of cyclopropylphenyl sulfoxide
In a dry Schlenk reaction tube, cyclopropylphenyl sulfide (0.25mmol) sulfide and PDI (0.5 mol%) as compound of formula A were added to methanol (2.0 mL). Next, a balloon was filled with oxygen and fixed to the top of the schlenk reaction tube. The reaction was performed at room temperature under atmospheric oxygen with 15W white CFL irradiation. After the reaction was completed, brine was added to the reaction. The aqueous phase was re-extracted with ethyl acetate. Synthetic organic extracts in Na2SO4The residue was separated by silica gel column chromatography (petroleum ether: ethyl acetate: 10:1), and purified to obtain a white viscous solid (yield: 85%; selectivity: 100%).1H NMR(400MHz,Chloroform-d)δ7.75–7.62(m,2H),7.58–7.48(m,3H),2.27(tt,J＝7.9,4.9Hz,1H),1.31–1.21(m,2H),1.09–1.01(m,1H),1.01–0.91(m,2H).
The reaction was carried out as described above using sulfide (0.25mmol) and perylene imide (0.5 mol%) in methanol (2 mL). The reaction mixture was stirred and irradiated with 15W white CFL at room temperature under an atmospheric oxygen atmosphere. The reaction is substrate extended under optimal conditions and for oxidation of sulfides, various alkyl and aryl sulfones yield 80-95% of the desired product. The method realizes the selective oxidation of the thioether catalyzed by the perylene bisimide under the visible light for the first time, successfully constructs the sulfoxide subbiology with high yield. In summary, we have developed a very mild and efficient method for achieving selective oxidation.
Example 19
Referring to example 1, the amounts of the catalysts used were changed to the amounts shown in table 1, and the reaction results were shown in table 1, except that the conditions were changed.
TABLE 1 Effect of the amounts of different PDI catalysts on the reaction
Example 20
Referring to example 1, the catalysts were replaced with the other catalysts shown in table 2, respectively, and the reaction results are shown in table 2, except that the conditions were not changed.
TABLE 2 Effect of different catalysts on the reaction
It should be understood that the above examples are only illustrative of the technical concept and features of the present invention, and that seven acres are provided to enable those skilled in the art to understand the present invention and not to limit the scope of the present invention at one time. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. A method for synthesizing sulfoxide compounds is characterized in that perylene imide compounds are used as catalysts in an organic solvent to catalyze thioether compounds to react with an oxidant under the irradiation of visible light to obtain sulfoxide compounds;
the oxidant is oxygen;
the perylene bisimide compound is a compound represented by a formula A, B, C, D shown in the following structure,
the molar equivalent of the perylene bisimide compound relative to the thioether compound is not less than 5 mol%.
2. The method of claim 1, wherein the method has a reaction equation as follows:
wherein R in the thioether compound1、R2Each independently selected from any one of deuterated methyl, unsubstituted or halogen-substituted C1-C6 straight-chain or branched alkyl, unsubstituted or halogen-substituted C3-C10 cycloalkyl, unsubstituted or substituted aromatic ring and aromatic heterocycle.
3. The method of claim 2, wherein R is1Or R2Is any one of the following: phenyl, methyl, ethyl, butyl, substituted or unsubstituted with one or more substituents; the substituent on the phenyl is halogen, -NO2、-OMe、-Me、-tBu.
4. The method according to any one of claims 1 to 3, wherein the organic solvent is one or more of an alcohol solvent, a halogenated hydrocarbon, an aromatic hydrocarbon, dimethyl sulfone, an ester, a heterocyclic aromatic hydrocarbon, an aliphatic hydrocarbon, an amide solvent and acetonitrile.
5. The method according to any one of claims 1 to 3, wherein the light source of visible light is a 5-50W LED light source.
6. The method of claim 5, wherein the light source has a color selected from the group consisting of red, green, blue, cyan, yellow, white, amber.
7. The method according to any one of claims 1 to 3, wherein the reaction is carried out at room temperature for 8 to 20 hours.
8. The method according to any one of claims 1-3, further comprising: after the reaction is finished, adding water and a solvent which cannot be mutually dissolved with the water into the reaction solution, separating the solution, further extracting the obtained water layer by using an organic solvent, combining the organic layers, removing the organic solvent in the organic layers to obtain a crude product, and purifying the crude product by using a chromatographic column.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910565960.5A CN110256307B (en) | 2019-06-27 | 2019-06-27 | Method for synthesizing sulfoxide compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910565960.5A CN110256307B (en) | 2019-06-27 | 2019-06-27 | Method for synthesizing sulfoxide compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110256307A CN110256307A (en) | 2019-09-20 |
| CN110256307B true CN110256307B (en) | 2021-01-29 |
Family
ID=67922171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910565960.5A Active CN110256307B (en) | 2019-06-27 | 2019-06-27 | Method for synthesizing sulfoxide compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110256307B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112409247B (en) * | 2020-11-20 | 2022-05-06 | 湖南生物机电职业技术学院 | Photocatalytic synthesis method of methyl heteroaryl sulfone compound |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205229A (en) * | 2006-12-20 | 2008-06-25 | 中国科学院化学研究所 | Dizotetracarboxylic dianiline compositions and preparation thereof |
| CN106588924A (en) * | 2016-11-23 | 2017-04-26 | 南昌大学 | Perfluoroalkyl-modified perylene imide and its preparation method |
| CN106939008A (en) * | 2016-12-31 | 2017-07-11 | 南京新月材料科技有限公司 | A kind of dissolubility Qiang perylene diimides and its synthetic method |
| CN108484456A (en) * | 2018-02-01 | 2018-09-04 | 浙江工业大学 | A kind of method of selectively oxidizing sulfur ether |
| CN108864153A (en) * | 2018-09-10 | 2018-11-23 | 河南湾流生物科技有限公司 | The preparation method and application of biologically active novel class drug molecule |
| CN109705002A (en) * | 2018-12-18 | 2019-05-03 | 江南大学 | A kind of photocatalytic synthesis at sulphur sulphones method |
-
2019
- 2019-06-27 CN CN201910565960.5A patent/CN110256307B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205229A (en) * | 2006-12-20 | 2008-06-25 | 中国科学院化学研究所 | Dizotetracarboxylic dianiline compositions and preparation thereof |
| CN106588924A (en) * | 2016-11-23 | 2017-04-26 | 南昌大学 | Perfluoroalkyl-modified perylene imide and its preparation method |
| CN106939008A (en) * | 2016-12-31 | 2017-07-11 | 南京新月材料科技有限公司 | A kind of dissolubility Qiang perylene diimides and its synthetic method |
| CN108484456A (en) * | 2018-02-01 | 2018-09-04 | 浙江工业大学 | A kind of method of selectively oxidizing sulfur ether |
| CN108864153A (en) * | 2018-09-10 | 2018-11-23 | 河南湾流生物科技有限公司 | The preparation method and application of biologically active novel class drug molecule |
| CN109705002A (en) * | 2018-12-18 | 2019-05-03 | 江南大学 | A kind of photocatalytic synthesis at sulphur sulphones method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110256307A (en) | 2019-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fan et al. | Ru (III)-catalyzed oxidative reaction in ionic liquid: an efficient and practical route to 2-substituted benzothiazoles and their hybrids with pyrimidine nucleoside | |
| CN111484452B (en) | Method for continuously preparing dihydro benzo [ j ] phenanthridine compound containing trifluoromethyl functional group by using microchannel reaction device | |
| CN108191729B (en) | A kind of synthetic method of thiosulfonic acid esters compound | |
| Xu et al. | Palladium-catalyzed direct ortho-ethoxycarbonylation of azobenzenes and azoxybenzenes with diethyl azodicarboxylate | |
| Li et al. | Nickel-catalyzed C–H direct amination of benzoxazoles with secondary Amines | |
| Wagh et al. | Cu (acac) 2 catalyzed oxidative C–H bond amination of azoles with amines under base-free conditions | |
| CN108164475B (en) | Method for catalytic synthesis of difluoromethyl-substituted linear aryl hetero-ketone | |
| CN106349147A (en) | Synthetic method of pyrrole derivatives | |
| CN110256307B (en) | Method for synthesizing sulfoxide compound | |
| Zhao et al. | Copper on charcoal: Cu 0 nanoparticle catalysed aerobic oxidation of α-diazo esters | |
| CN110357801A (en) | A kind of method that three component reaction of catalysis of iodine synthesizes nitrogenous five member ring heterocyclic compound | |
| CN112442008B (en) | Method for preparing 1, 4-dithiine and thiophene compounds by regulating elemental sulfur and active internal alkyne at temperature and conversion reaction of compound | |
| Luo et al. | Oxidation of alcohols to carbonyl compounds with molecular iodine in the presence of potassium tert-butoxide | |
| CN110372613B (en) | Preparation method of 2,3, 6-trisubstituted pyrazine nitroxide compound | |
| CN111995554A (en) | Method for preparing asymmetric organic selenium ether compound by metal-free chemical oxidation method | |
| M Vahdat et al. | Sulfonated organic heteropolyacid salts: Recyclable green solid catalysts for the highly efficient and green synthesis of bis (indolyl) methanes in Water | |
| CN113666826A (en) | Method for methoxylation of aryl or heteroaryl | |
| CN108658835B (en) | Method for synthesizing indole-2-ketone compound | |
| CN111777564A (en) | Method for synthesizing quinazolinone compound through photocatalytic alcohol oxidation in aqueous phase | |
| CN109796492A (en) | A kind of preparation method of the phosphorus nitrence compound of cadmium sulfide catalysis | |
| CN110627823A (en) | Method for catalyzing arylamine to generate deamination boric acid esterification or halogenation | |
| CN107739322B (en) | Synthetic method of sulfonamide compound | |
| CN112159344B (en) | Synthesis method of 1, 3-dimethyl-3-hydroxymethyl indoline-2-ketone compound | |
| CN110143933B (en) | Method for directly synthesizing epoxy compound from benzyl bromide compound | |
| CN105712851B (en) | A kind of preparation method of the two arone compound containing betanaphthyl |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |