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Efficient method for selectively synthesizing 2-hydroxybenzene sulfur ether compound

A technology for hydroxyphenylene sulfide and compound, which is applied in the field of biosynthesis, can solve the problems of low reaction efficiency, many reaction steps, and limited reaction application range, and achieves high chemical selectivity, mild synthesis conditions, and controllable chemical selectivity. Effect

Inactive Publication Date: 2016-03-02
JIYANG COLLEGE OF ZHEJIANG A & F UNIV
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  • Description
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Problems solved by technology

The known synthetic method of 2-hydroxyphenylene sulfide is mainly catalyzed by transition metals, such as Pd, Pt, etc. to catalyze thiophenol and halogenated benzene, and obtain through multi-step coupling, oxidation, and hydrolysis, and there are many reaction steps and reaction Disadvantages such as low efficiency and not wide range of reaction applications

Method used

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  • Efficient method for selectively synthesizing 2-hydroxybenzene sulfur ether compound
  • Efficient method for selectively synthesizing 2-hydroxybenzene sulfur ether compound
  • Efficient method for selectively synthesizing 2-hydroxybenzene sulfur ether compound

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Embodiment 1: Preparation of 3a product

[0030] In a 25 mL round bottom flask at room temperature, add 3 mmol, 330 mg thiophenol and 3.6 mmol, 630 mg iodobenzene, 0.25 equiv, 140 mg cuprous iodide, 0.25 equiv, 140 mg enaminone ligand, 2 equiv, 978 mg cesium carbonate, In dimethyl sulfoxide 10mL solvent 120 o The reaction was carried out under C conditions for 8 hours. After the reaction was completed and cooled, 10 mL of saturated NaCl aqueous solution was added to the system, extracted 3 times with ethyl acetate, 10 mL each time, the organic phases were combined, and washed with anhydrous NaCl 2 SO 4 After drying, the solvent was evaporated, and 200-300 mesh silica gel column chromatography was used to obtain 515 mg of the 2-hydroxyphenyl sulfide with a yield of 85%. H NMR spectrum see figure 1 .

[0031] 1 HNMR (500MHz, d 6 -DMSO): δ9.96(s,1H),7.33-7.30(m,2H),7.23-7.21(q, J =7.1Hz,1H),7.20-7.17(m,3H),7.13-7.11(q, J =7.5Hz,1H),6.94-6.93(d, J =7.4Hz,1H),6.81-6...

Embodiment 2

[0033] Embodiment 2: Preparation of 3b product

[0034] In a 25 mL round bottom flask at room temperature, add 3 mmol, 372 mg 4-methylthiophenol and 3.6 mmol, 630 mg iodobenzene, 0.25 equiv, 140 mg cuprous iodide, 0.25 equiv, 140 mg enaminone ligand, 2 equiv, 978 mg Cesium carbonate, in dimethyl sulfoxide 10mL solvent 120 o The reaction was carried out under the condition of C for 8 hours. After the reaction was completed and cooled, 10 mL of saturated NaCl aqueous solution was added to the system, extracted 3 times with ethyl acetate, 10 mL each time, the organic phases were combined, and washed with anhydrous NaCl 2 SO 4 After drying, the solvent was distilled off, and 577 mg of the 4-methyl-2-hydroxyphenyl sulfide was obtained by 200-300 mesh silica gel column chromatography, with a yield of 89%. H NMR spectrum see figure 2 .

[0035] 1 HNMR (500MHz, d 6 -DMSO): δ9.79(s,1H),7.28-7.25(d, J =7.3Hz,2H),7.16-7.12(d, J =7.2Hz,2H),7.09-7.08(d, J =7.9Hz,2H),6.77(s,1H),6....

Embodiment 3

[0037] Embodiment 3: the preparation of 3c product

[0038] Add 3mmol, 432mg 4-chlorothiophenol and 3.6mmol, 630mg iodobenzene, 0.25equiv, 140mgCuI, 0.25equiv, 140mg enaminone ligand, 2equiv, 978mg cesium carbonate in a 25mL round bottom flask at room temperature Methyl sulfoxide 10mL solvent 120 oThe reaction was carried out under the condition of C for 8 hours. After the reaction was completed and cooled, 10 mL of saturated NaCl aqueous solution was added to the system, extracted 3 times with ethyl acetate, 10 mL each time, the organic phases were combined, and extracted with NaCl-free 2 SO 4 After drying, the solvent was distilled off, and 651 mg of the 4-chloro-2-hydroxyphenylsulfide was obtained by 200-300 mesh silica gel column chromatography, with a yield of 92%. H NMR spectrum see image 3 .

[0039] 1 HNMR (500MHz, d 6 -DMSO): δ10.52(s,1H),7.37-7.32(d, J =8.5Hz,2H),7.26-7.25(d, J =8.0Hz,1H),7.23-7.21(m,2H),7.09-7.07(d, J =8.5Hz,1H),6.96-6.95(d, J =2.0Hz,1H),...

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Abstract

The invention provides an efficient method for selectively synthesizing a 2-hydroxybenzene sulfur ether compound. The method includes the steps of making a thiophenol compound shown in the formula (I) and an aryl halide compound shown in the formula (II) sufficiently react in a reaction medium with dimethyl sulfoxide as solvent under the effects of a catalyst, ligand and alkali carbonate to prepare a reagent, and conducting postprocessing on the reagent to prepare the 2-hydroxybenzene sulfur ether compound, wherein cuprous iodide serves as the catalyst, enaminone serves as the ligand, and cesium carbonate serves as the alkali carbonate. R1 in the formula (I) or the formula (II) is selected from one of alkyl and halogen. R2 in the formula (II) or the formula (III) is selected from one of methoxyl, halogen and trifluoromethyl. Raw materials can be easily obtained, the synthesis condition is gentle, the chemical selectivity is high and controllable, cost is saved, the requirements for devices are low, solvent and water can dissolve each other, postprocessing is convenient, the catalytic system is wide in adaptability, and the method is suitable for large-scale industrialized production.

Description

technical field [0001] The invention belongs to the technical field of biosynthesis, and in particular relates to a method for efficiently and selectively synthesizing 2-hydroxyphenylene sulfide compounds. Background technique [0002] 2-Hydroxyphenyl sulfide compounds are an important class of organic compounds, which have extensive and important applications in the field of organic chemistry. It is widely used in the synthesis of sulfur-containing aromatic compounds and natural products, and it is also the molecular skeleton in many organic compounds with pharmaceutical activity. The known synthetic method of 2-hydroxyphenyl sulfide is mainly catalyzed by transition metals, such as Pd, Pt, etc. to catalyze thiophenol and halogenated benzene, and obtain through multi-step coupling, oxidation, and hydrolysis, and there are many reaction steps and reaction The disadvantages are low efficiency and not wide range of reaction applications. The method realizes the high-efficien...

Claims

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Application Information

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IPC IPC(8): C07C319/14C07C323/20
Inventor 徐润生徐锦
Owner JIYANG COLLEGE OF ZHEJIANG A & F UNIV
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