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

A technology of cyclohexenone and derivatives, applied in the field of preparation of thiophene derivatives, to achieve the effects of reducing the total cost, increasing the total yield of synthesis, and simple reaction steps

Active Publication Date: 2017-09-08
SHANXI UNIV
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AI Technical Summary

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

Method used

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

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] Example 1: Synthesis of 3-(3-methylthiophen-5-yl)cyclohex-2-enone

[0043] (1) 3-methylthiophene (0.024ml, 0.25mmol), cyclohexenone (0.072ml, 0.75mmol), palladium chloride (0.0044g, 0.0025mmol), N-acetylglycine (0.0029g, 0.0025mmol ), silver carbonate (0.1723g, 0.625mmol), silver hexafluoroantimonate (0.0172g, 0.05mmol), dimethylsulfoxide (0.05ml), 1,1,1,3,3,3-hexafluoro-2 -Propanol (0.05ml), 1,4-dioxane (1ml), stirred evenly in a clean and dry airtight reaction tube, heated to 60°C, and reacted for 24 hours.

[0044] (2) After the reaction is completed, cool the reaction tube to room temperature, add 40ml of ethyl acetate to dilute the reaction system and transfer it to a 100ml separatory funnel, add 20ml of saturated ammonium chloride aqueous solution, shake, let it stand, and remove the lower water phase Afterwards, add 20ml of saturated saline again, shake, let stand, remove the lower water phase, the organic phase is dried with anhydrous sodium sulfate, remove the...

Embodiment 2

[0045] Example 2: Synthesis of 3-(5-phenylthiophen-2-yl)cyclohex-2-enone

[0046] (1) O-phenylthiophene (0.0401g, 0.25mmol), cyclohexenone (0.072ml, 0.75mmol), palladium chloride (0.0044g, 0.0025mmol), N-acetylglycine (0.0029g, 0.0025mmol), Silver carbonate (0.1723g, 0.625mmol), silver hexafluoroantimonate (0.0172g, 0.05mmol), dimethylsulfoxide (0.05ml), 1,1,1,3,3,3-hexafluoro-2-propane Alcohol (0.05ml), 1,4-dioxane (1ml), stirred evenly in a clean and dry airtight reaction tube, heated to 60°C, and reacted for 24 hours.

[0047] (2) After the reaction is completed, cool the reaction tube to room temperature, add 40ml of ethyl acetate to dilute the reaction system and transfer it to a 100ml separatory funnel, add 20ml of saturated ammonium chloride aqueous solution, shake, let it stand, and remove the lower water phase Afterwards, add 20ml of saturated saline again, shake, let stand, remove the lower water phase, the organic phase is dried with anhydrous sodium sulfate, remov...

Embodiment 3

[0048] Example 3: Synthesis of 3-(4-methoxythiophen-2-yl)cyclohex-2-enone

[0049] (1) 3-methoxythiophene (0.025ml, 0.25mmol), cyclohexenone (0.072ml, 0.75mmol), palladium chloride (0.0044g, 0.0025mmol), N-acetylglycine (0.0029g, 0.0025 mmol), silver carbonate (0.1723g, 0.625mmol), silver hexafluoroantimonate (0.0172g, 0.05mmol), dimethylsulfoxide (0.05ml), 1,4-dioxane (1ml), in clean dry Stir evenly in a sealed reaction tube, heat to 60°C, and react for 24 hours.

[0050] (2) After the reaction is completed, cool the reaction tube to room temperature, add 40ml of ethyl acetate to dilute the reaction system and transfer it to a 100ml separatory funnel, add 20ml of saturated ammonium chloride aqueous solution, shake, let it stand, and remove the lower water phase Afterwards, add 20ml of saturated saline again, shake, let stand, remove the lower water phase, the organic phase is dried with anhydrous sodium sulfate, remove the solvent under reduced pressure, and the residue is s...

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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,...

Claims

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Application Information

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IPC IPC(8): C07D333/22C07D333/32C07D333/28C07D333/38
CPCC07D333/22C07D333/28C07D333/32C07D333/38
Inventor 文振康宋婷婷刘宇芳钞建宾
Owner SHANXI UNIV
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