Preparation method of 3-(thiophene-2-yl)hexanaphthene-2-ketene derivatives

Abstract

The invention relates to the technical field of a preparation method of thiophene derivatives, in particular to a preparation method of 3-(thiophene-2-yl)hexanaphthene-2-ketene derivatives. The preparation method of the 3-(thiophene-2-yl)hexanaphthene-2-ketene derivatives comprises the following steps: (1) adding cyclohexenone, thiophene or substituted thiophene, palladium chloride, silver carbonate, N-acetoglycocoll and silver hexafluoroantimonate into a reactor sequentially according to the molar ratio of 3:1:0.1:2.5:0.1:0.2, adding a solvent to dissolve the reactants, mixing uniformly at a room temperature, and reacting at 60 to 120 DEG C for 5 to 48 hours; (2) after the reaction, cooling the reactor to a room temperature, dissolving with ethyl acetate, washing with a saturated ammonium chloride aqueous solution and a saturated sodium chloride aqueous solution sequentially, drying the organic phase by using anhydrous sodium sulfate, filtering and rotating on a rotary evaporator to remove the solvent; (3) separating and purifying the residues through silica-gel column chromatography after the solvent is removed through rotation, collecting a target product, performing rotary evaporation to remove the solvent, and pumping and drying by an oil pump.

Description

technical field [0001] The invention relates to the technical field of preparation methods of thiophene derivatives, in particular to a preparation method of 3-(thiophen-2-yl)cyclohex-2-enone derivatives. [0002] technical background [0003] Thiophene is an important aromatic heterocyclic compound, and its derivatives are used as key components in various bioactive molecules and functional materials [Ref: (a) Acc. Chem. Res. 2001, 34, 359–369; (b) Angew. Chem., Int. Ed. 2005, 44, 5452–5456.]. Substituted phenolic derivatives are very important chemical intermediates widely used in the preparation of various drugs, pesticides, polymers and fine chemicals. However, meta-substituted phenolic compounds are usually difficult to synthesize due to the strong ortho-para effect of phenolic hydroxyl groups. The use of 3-substituted cyclohex-2-enone derivatives developed in recent years to prepare meta-substituted phenolic compounds through further oxidation (Angew.Chem.Int.Ed.2013,...

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Problems solved by technology

The preparation of 3-substituted cyclohex-2-enones by palladium-catalyzed C-H / C-H oxidative coupling reaction is undoubtedly the most economical and concise reaction route. In the Heck reaction, the generated palladium intermediate and the hydrogen on the β-carbon must be on the same side for the β-hydrogen elimination reaction, and the tension of the ring makes the free rotation of the carbon-palladium bond limited (Angew.Chem.Int.Ed. 2013,52,3672–3675), the transition metal-catalyzed direct C-H / C-H oxidative coupling reaction of cyclohexenone and heterocycle to construct 3-heterocyclylcyclohex-2-enone derivatives is still unresolved, so It is urgent to develop a method based on direct C-H / C-H oxidative coupling reaction to construct 3-heterocyclylcyclohex-2-enone derivatives, followed by oxidation under acidic conditions to obtain 3-heterocyclic phenol derivatives

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