Method for synthesizing diphenylacetylene by utilizing calcium carbide

Abstract

The invention belongs to the technical field of organic synthesis intermediate, medicine and liquid crystal material, in particular, relates to a method for synthesizing diphenylacetylene by utilizing calcium carbide. The method comprises the following specific steps: adding toluene, iodobenzene, cesium carbonate, cuprous iodide, ferron, N,N'-dimethylethylenediamine, and calcium carbide into a reactor, stirring and reacting at the temperature of between 140 and 146 DEG C for 115-125 hours; water processing the reactant after finishing the reaction, extracting with ethyl acetate, washing the organic layer with saturated salt water, and drying with anhydrous sodium sulfate, and them obtaining crude product after decompression evaporating solvent; separating and purifying the crude product by column chromatography to obtain the required product. Molar ratio of calcium carbide to iodobenzene is (2-10):1; molar ratio of cesium carbonate to iodobenzene is (1.5-3):1; molar ratio of cuprous iodide to iodobenzene is (0.05-0.3):1; molar ratio of ferron to iodobenzene is (0.05-0.3):1; and molar ratio of N,N'-dimethylethylenediamine to iodobenzene is (0.05-0.3):1. The diphenylacetylene synthesized by the method can be applied to organic synthesis, liquid crystal material and pharmic synthesis intermediates. The invention takes calcium carbide as raw material and ferric chloride as catalyst. The invention has easily obtained raw material, low cost, simple technology, and easy industrialization.

Description

technical field

[0001] The invention belongs to the technical field of organic synthesis intermediates, liquid crystal materials and medicines, and specifically relates to a method for synthesizing tolan by using calcium carbide. Background technique

[0002] Diphenylacetylene compounds have important chemical activity and have broad application prospects in the fields of organic synthesis, drug synthesis and liquid crystal materials. Among them, the tolanyl liquid crystal material has a large threshold value and low viscosity, can improve the birefringence and clearing point of the mixed liquid crystal, can reduce the viscosity of the liquid crystal, and improve the response speed of the liquid crystal, and has been widely used in the synthesis of high-grade liquid crystals.

[0003] At present, the preparation methods of tolanyl compounds mainly include: palladium-catalyzed coupling reaction of aryl halide and aryne, halogenation addition and elimination of 1,2-diarylethen...

Examples

Embodiment 1

[0017] Embodiment 1: the synthesis of ferric chloride catalyzed tolan

[0018]

[0019] Add toluene 10mL, cuprous iodide 95mg (0.5mmol), ferric chloride 80mg (0.5mmol), N,N'-dimethylethylenediamine (DMEDA) 44mg (0.5mmol), iodine Benzene 510mg (2.5mmol), calcium carbide 640mg (10mmol), cesium carbonate 1628mg (5mmol), magnetic stirring reaction at 140-146°C. After 120 hours the reaction was complete and the reactant was treated with water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (ethyl acetate / petroleum ether=1 / 35) to obtain 66 mg of a white solid. Yield 29.7%. Its NMR data are as follows: 1 H NMR (400MHz, CDCl 3 ): δ = 7.60-7.57 (m, 4H), 7.42-7.35 (m, 6H).

Embodiment 2

[0020] Embodiment 2: the synthesis of ferric sulfate catalyzed tolan

[0021]

[0022] Add 10 mL of toluene, 95 mg (0.5 mmol) of cuprous iodide, 200 mg (0.5 mmol) of ferric sulfate, 44 mg (0.5 mmol) of N,N'-dimethylethylenediamine (DMEDA), and 510 mg of iodobenzene into a 50 mL reaction test tube (2.5mmol), calcium carbide 640mg (10mmol), cesium carbonate 1628mg (5mmol), magnetic stirring reaction at 140-146°C. After 120 hours the reaction was complete and the reactant was treated with water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain a crude product, which was purified by column chromatography (ethyl acetate / petroleum ether=1 / 35) to obtain 50 mg of a white solid. Yield 22.5%.

Embodiment 3

[0023] Embodiment 3: the synthesis of the tolan of iron acetylacetonate catalyst

[0024]

[0025] Add 10 mL of toluene, 95 mg (0.5 mmol) of cuprous iodide, 175 mg (0.5 mmol) of iron acetylacetonate, 44 mg (0.5 mmol) of N,N'-dimethylethylenediamine (DMEDA), and 44 mg (0.5 mmol) of iodobenzene into a 50 mL reaction test tube. 510mg (2.5mmol), calcium carbide 640mg (10mmol), cesium carbonate 1628mg (5mmol), magnetic stirring reaction at 140-146°C. After 120 hours the reaction was complete and the reactant was treated with water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (ethyl acetate / petroleum ether=1 / 35) to obtain 55 mg of a white solid. Yield 24.7%.

technical field

[0001] The invention belongs to the technical field of organic synthesis intermediates, liquid crystal materials and medicines, and specifically relates to a method for synthesizing tolan by using calcium carbide. Background technique

[0002] Diphenylacetylene compounds have important chemical activity and have broad application prospects in the fields of organic synthesis, drug synthesis and liquid crystal materials. Among them, the tolanyl liquid crystal material has a large threshold value and low viscosity, can improve the birefringence and clearing point of the mixed liquid crystal, can reduce the viscosity of the liquid crystal, and improve the response speed of the liquid crystal, and has been widely used in the synthesis of high-grade liquid crystals.

[0003] At present, the preparation methods of tolanyl compounds mainly include: palladium-catalyzed coupling reaction of aryl halide and aryne, halogenation addition and elimination of 1,2-diarylethen...

Examples

Embodiment 1

[0017] Embodiment 1: the synthesis of ferric chloride catalyzed tolan

[0018]

[0019] Add toluene 10mL, cuprous iodide 95mg (0.5mmol), ferric chloride 80mg (0.5mmol), N,N'-dimethylethylenediamine (DMEDA) 44mg (0.5mmol), iodine Benzene 510mg (2.5mmol), calcium carbide 640mg (10mmol), cesium carbonate 1628mg (5mmol), magnetic stirring reaction at 140-146°C. After 120 hours the reaction was complete and the reactant was treated with water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (ethyl acetate / petroleum ether=1 / 35) to obtain 66 mg of a white solid. Yield 29.7%. Its NMR data are as follows: 1 H NMR (400MHz, CDCl 3 ): δ = 7.60-7.57 (m, 4H), 7.42-7.35 (m, 6H).

Embodiment 2

[0020] Embodiment 2: the synthesis of ferric sulfate catalyzed tolan

[0021]

[0022] Add 10 mL of toluene, 95 mg (0.5 mmol) of cuprous iodide, 200 mg (0.5 mmol) of ferric sulfate, 44 mg (0.5 mmol) of N,N'-dimethylethylenediamine (DMEDA), and 510 mg of iodobenzene into a 50 mL reaction test tube (2.5mmol), calcium carbide 640mg (10mmol), cesium carbonate 1628mg (5mmol), magnetic stirring reaction at 140-146°C. After 120 hours the reaction was complete and the reactant was treated with water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain a crude product, which was purified by column chromatography (ethyl acetate / petroleum ether=1 / 35) to obtain 50 mg of a white solid. Yield 22.5%.

Embodiment 3

[0023] Embodiment 3: the synthesis of the tolan of iron acetylacetonate catalyst

[0024]

[0025] Add 10 mL of toluene, 95 mg (0.5 mmol) of cuprous iodide, 175 mg (0.5 mmol) of iron acetylacetonate, 44 mg (0.5 mmol) of N,N'-dimethylethylenediamine (DMEDA), and 44 mg (0.5 mmol) of iodobenzene into a 50 mL reaction test tube. 510mg (2.5mmol), calcium carbide 640mg (10mmol), cesium carbonate 1628mg (5mmol), magnetic stirring reaction at 140-146°C. After 120 hours the reaction was complete and the reactant was treated with water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (ethyl acetate / petroleum ether=1 / 35) to obtain 55 mg of a white solid. Yield 24.7%.

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