CN113880738A - Method for synthesizing thioether compound - Google Patents
Method for synthesizing thioether compound Download PDFInfo
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- CN113880738A CN113880738A CN202110978358.1A CN202110978358A CN113880738A CN 113880738 A CN113880738 A CN 113880738A CN 202110978358 A CN202110978358 A CN 202110978358A CN 113880738 A CN113880738 A CN 113880738A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
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- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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Abstract
The invention discloses a method for synthesizing thioether compounds, belonging to the technical field of organic matter synthesis; the invention realizes the synthesis of thioether compounds with diversified structures by catalyzing sulfoxide deoxidation and reduction by rare earth, and particularly prepares the thioether compounds by taking various sulfoxide compounds as raw materials and phenylsilane as a reducing agent in a rare earth catalytic system. The method has the advantages of wide raw material source or easy preparation, simple and convenient operation, controllable selectivity, high yield, mild condition, no need of organic solvent and wide universality.
Description
Technical Field
The invention relates to the technical field of thioether compound synthesis, in particular to a method for synthesizing a thioether compound.
Background
Thioether compounds are important organic compounds and organic synthesis intermediates, are important components of natural products and medicaments, and have unique optical properties. It occupies a very important position in organic synthesis. Therefore, the development of new methods for the synthesis of various and highly efficient thioether compounds has been an important issue in organic synthetic chemistry.
In the art of preparing thioether compounds, the conventional method of reducing sulfoxides to sulfides involves the use of lower valent metal species such as metal hydride reagents, halides, phosphorus compounds, Woollin's reagent, and phosphines. However, such methods suffer from the presence of such agents as reducing agents that are not readily available [ e.g., (NH)4)4Mo2Cl:NH4ClH2O]Poor chemical selectivity (e.g., diisobutylaluminum hydride), low pH value of the reaction system (e.g., reductive halogenation system of hydrogen halide), and high reaction temperature (e.g., Woollin's reagent). The literature reports that Woollins reagent can be used for reducing diphenyl sulfoxide, the separation yield is up to 99%, but the chemical selectivity is poor, and the reaction cannot occur during the reduction of other sulfoxide compounds, so that the method has certain limitation.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for synthesizing thioether compounds, which has wide raw material sources and simple and convenient operation, and can synthesize thioether compounds with high selectivity by taking various sulfoxide compounds as raw materials.
The purpose of the invention is realized by the following technical scheme:
a method for synthesizing thioether compound is characterized in that under the protection of nitrogen and the existence of rare earth catalyst, a compound shown as a formula I is used as a raw material, and a thioether compound shown as a formula II is prepared through a deoxidation reduction reaction; the chemical reaction equation is as follows:
in the formula, the formula I is various sulfoxide compounds,
wherein R is1Is phenyl, substituted phenyl, benzyl (phenylmethyl), alkyl;
R2is phenyl, substituted phenyl, benzyl, alkyl;
preferably, said diluentThe clay catalyst is selected from Ln [ N (SiMe)3)2]3Ln is Sc, Y, lanthanide series all elements and rare earth alkyl complexes.
Preferably, the amount of substance of the compound of formula I: amount of substance PhSiH 3: the amount of the rare earth catalyst substance is 1.0: 3.0: 0.1.
preferably, the reaction temperature for preparing the thioether compound is 120-130 ℃, and the reaction time is 24-48 h.
The reaction mechanism of the present invention is shown in FIG. 2:
firstly, reacting trisilicamine rare earth complex with phenylsilane to obtain a rare earth hydride intermediate A, carrying out coordination activation on the rare earth hydride intermediate A and sulfoxide, carrying out double decomposition reaction to obtain an intermediate B, further reacting the intermediate B with phenylsilane to obtain a target product thioether, and releasing the hydride intermediate A to complete catalytic cycle.
The invention has the beneficial effects that:
(1) the reaction universality is good, the atom economy is high, the bonding efficiency is high, and the separation yield is high;
(2) the reaction conditions are mild and no large amount of/fussy additives are needed;
(3) the rare earth silicon-amino complex catalyst is moderate in price, commercially available and easy to obtain;
(4) the reaction does not need an organic solvent, and is green and environment-friendly.
To sum up: the invention realizes the synthesis of the thioether compound by catalyzing sulfoxide to deoxidize and reduce with the rare earth metal complex for the first time, and provides an important reference for the construction of the thioether compound. In addition, since rare earth catalysts are very oxygen-philic, catalytic cycling is difficult to achieve under typical reaction conditions, rare earth catalysts are generally not used in the preparation of thioether compounds. According to the invention, by adding a silane reagent which is more oxygen-philic, the deoxidation reduction reaction of the sulfoxide catalyzed by the rare earth is realized, and the problem that rare earth catalysis circulation is difficult to pass in the prior art is solved. Meanwhile, due to the characteristics of simple raw material source, low cost and no pollution, the method is very easy to obtain commercial success.
Drawings
FIG. 1: a flow diagram of the present invention;
FIG. 2: reaction mechanism diagram of the invention;
FIG. 3: the reaction conditions of the present invention are shown in the figure.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited to the following.
The synthesis of the thioether compound is carried out according to the process shown in figure 1, and the specific implementation mode is as follows:
example 1
Preparation of diphenyl sulfide, the structural formula is as follows:
under the protection of nitrogen, add raw materials diphenyl sulfoxide (0.3mmol) and phenylsilane (0.9mmol), catalyst Y [ N (SiMe)3)2]3(0.03mmol) and reacted at 120 deg.c for 24 hr to obtain product in 85% yield.
Performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1H NMR(CDCl3,500MHz,ppm):δ7.35(d,J＝7.5Hz,4H),7.31(t,J＝7.5Hz,4H),7.25(t,J＝7.5Hz,2H).
13C NMR(CDCl3,125MHz,ppm):δ135.93,131.19,129.33,127.18.
example 2
Preparation of 4,4' -dimethylsulfide sulfide, structural formula is as follows:
under the protection of nitrogen, adding raw materials of 4,4' -dimethyl sulfoxide (0.3mmol) and phenylsilane (0.9mmol) and a catalyst Y [ N (SiMe)3)2]3(0.03mmol) and reacted at 120 deg.c for 24 hr to obtain product in 84% yield.
Performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1H NMR(CDCl3,500MHz,ppm):δ7.25(d,J＝8.2Hz,4H),7.11(d,J＝8.2Hz,4H),2.33(s,6H).13C NMR(CDCl3,125MHz,ppm)δ137.00,132.78,131.18,130.03,21.20.
example 3
Preparation of 4,4' -dichlorodiphenyl sulfide, structural formula is as follows:
under the protection of nitrogen, adding raw material 4,4' -dichlorodiphenyl sulfoxide (0.3mmol) and phenylsilane (0.9mmol), and catalyst Y [ N (SiMe)3)2]3(0.03mmol) and reacted at 120 deg.c for 48 hr to obtain product in 90% yield.
Performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1H NMR(CDCl3,400MHz,ppm):δ7.27-7.29(m,4H),7.24-7.26(m,4H).13C NMR(CDCl3,125MHz,ppm):δ134.08,133.62,132.45,129.64.
example 4
Preparation of dibenzyl sulfide, the structural formula is as follows:
under the protection of nitrogen, adding raw materials of dibenzyl sulfoxide (0.3mmol), phenylsilane (0.9mmol) and catalyst Y [ N (SiMe)3)2]3(0.03mmol) and reacted at 120 deg.c for 24 hr to obtain 93% isolated product.
Performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1H NMR(CDCl3,400MHz,ppm):δ7.24-7.16(m,10H),3.50(s,4H).13C NMR(CDCl3,125MHz,ppm):δ138.27,129.13,128.60,127.10,35.71
example 5
The preparation of 4-methyl diphenyl sulfide has the following structural formula:
under the protection of nitrogen, adding raw material 4-methyl diphenyl sulfoxide (0.3mmol), phenylsilane (0.9mmol) and catalyst Y [ N (SiMe)3)2]3(0.03mmol) and reacted at 120 deg.c for 24 hr to obtain product in 85% yield.
Performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1H NMR(CDCl3,400MHz,ppm):δ7.34-7.14(m,9H),2.36(s,3H).13C NMR(CDCl3,125MHz,ppm):δ＝137.7,137.2,132.4,131.4,130.2,129.9,129.2,126.5,21.2.
example 6
The preparation of 4-bromothioanisole has the following structural formula:
under the protection of nitrogen, adding raw material 4-bromophenyl methyl sulfoxide (0.3mmol), phenylsilane (0.9mmol) and catalyst Y [ N (SiMe)3)2]3(0.03mmol) and reacted at 130 deg.c for 24 hr to obtain product in 81% yield.
Performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1H NMR(CDCl3,400MHz,ppm):δ7.33(d,J＝8.6Hz,2H),7.10(d,J＝8.6Hz,2H),2.46(s,3H).13C NMR(CDCl3,125MHz,ppm):δ138.3,132.3,128.8,119.2,16.7.
example 7
The preparation of 4-chloro-thioanisole has the following structural formula:
under the protection of nitrogen, add raw materials 4-chlorophenyl methyl sulfoxide (0.3mmol) and phenylsilane (0.9mmol), catalyst Y [ N (SiMe)3)2]3(0.03mmol) and reacted at 130 deg.c for 24 hr to obtain 89% product.
Performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1H NMR(CDCl3,400MHz,ppm):δ7.26(d,J＝8.7Hz,2H),7.18(d,J＝8.7Hz,2H),2.47(s,3H).13C NMR(CDCl3,125MHz,ppm):δ137.3,131.0,128.9,128.0,16.2.
comparative example
Fangwei Ding et al developed a toluene solvent, B (C) in 20176Fs)3And a phenylsilane system to catalytically reduce the sulfoxide to produce the thioether compound with an isolation yield of between 60 and 82 percent.
Analysis of results
First, as can be seen from examples 1 to 7 and comparative examples, the isolation yields of the thioether compounds prepared by the present invention are all higher than 80%, even more than 90%, while the highest isolation yield of the product in the comparative example is 82%, which is much lower than that of the present invention; the reaction raw material of the comparative example is aryl alkyl sulfoxide, while the raw material of the invention is various sulfoxide compounds, so that the comparative example has low reaction selectivity and certain limitation.
Selection of reaction conditions in the present invention (see FIG. 3)
As can be seen from fig. 3:
(1) the sulfoxide compound and the phenylsilane can perform deoxidation and reduction reaction under the action of a rare earth catalyst to prepare the thioether compound, and the rare earth catalyst is selected from Ln [ N (SiMe)3)2]3Ln is any one of Sc, Y and lanthanide elements or any one of rare earth alkyl complexes, and in the preparation process, a reducing agent and a catalyst are easy to obtain, the chemical selectivity is strong, the reaction temperature is moderate, and the synthesis of thioether chemicals can be smoothly realized.
(2) When rare earth catalyst is Y [ N (SiMe)3)2]3When the reaction temperature is 120 ℃ and the reaction time is 24 hours, the separation yield of the reaction of the sulfoxide compound and the phenylsilane is higher than 80 percent, and the high separation yield in the prior art can be achieved or higher.
The foregoing is merely a preferred embodiment of the invention, it is to be understood that the invention is not limited to the forms disclosed herein, but is not intended to be exhaustive or to limit the invention to other embodiments, and to various other combinations, modifications, and environments and may be modified within the scope of the inventive concept as expressed herein, by the teachings or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012121845A (en) * | 2010-12-09 | 2012-06-28 | Daicel Corp | Method for producing sulfide by deoxygenation of sulfoxide |
| CN110803995A (en) * | 2019-10-16 | 2020-02-18 | 温州医科大学 | A method for synthesizing tertiary amine derivatives by the hydroboration reaction of rare earth catalyzed tertiary amides |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012121845A (en) * | 2010-12-09 | 2012-06-28 | Daicel Corp | Method for producing sulfide by deoxygenation of sulfoxide |
| CN110803995A (en) * | 2019-10-16 | 2020-02-18 | 温州医科大学 | A method for synthesizing tertiary amine derivatives by the hydroboration reaction of rare earth catalyzed tertiary amides |
Non-Patent Citations (5)
| Title |
|---|
| PENGQING YE 等: "Homoleptic Bis(trimethylsilyl)amides of Yttrium Complexes Catalyzed Hydroboration Reduction of Amides to Amines" * |
| STEPHAN ENTHALER 等: "Reduction of Sulfoxides to Sulfides in the Presence of Copper" * |
| STEPHAN ENTHALER: "A Facile and Efficient Iron-Catalyzed Reduction of Sulfoxides to Sulfides" * |
| STEPHAN ENTHALER: "A straightforward zinc-catalysed reduction of sulfoxides to sulfides" * |
| 李伟林 等: "亚砜脱氧还原方法研究进展" * |
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