hex-5-ynoyl chloride

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 2-allyl-6-t-butylphenol (0.57 g; 3 mmol) in dry CH2Cl2 (12 ml) is cooled to -78° C., and 5-hexynoyl chloride (0.43 g; 3.3 mmol) is added via syringe, followed by SnCl4 (0.375 ml) added dropwise via syringe, with stirring under Argon. After 30 min the reaction is allowed to warm to 0° C. and is stirred at that temperature for 5 min; it is then quenched with ca 1 ml of 3N HCl. The reaction is poured into 100 ml water and extracted with 3×50 ml portions of ether. The combined ether layers are washed with 150 ml portions of water until the aqueous layer is neutral (pH test). The ether layer is dried (MgSO4), filtered, and concentrated in vacuo to give crude product, which is chromatographed with 20:1 hexane/EtOAc, giving 0.64 g 2-allyl-4-(5-hexynoyl)-6-t-butylphenol (77% yield). The product is recrystallized from hexane at 0° C. to give crystals melting at 62°-63° C. added dropwise via syringe is stirred at that temperature for 5 min it is then quenched with ca 1 ml of 3N HCl The reaction is poured into 100 ml water extracted with 3×50 ml portions of ether The combined ether layers are washed with 150 ml portions of water until the aqueous layer The ether layer is dried (MgSO4) filtered concentrated in vacuo to give crude product, which is chromatographed with 20:1 hexane/EtOAc

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 2-tert-butyl-6-methylphenol (1.2 g, 7.3 mmol) in methylene chloride (28 ml, 1.1 equiv.), stirred under argon at -78° C., is added 5-hexynoyl chloride (1.0 g) followed by tin tetrachloride (0.93 mL, 1.1 equiv.). After stirring 30 minutes at -78° C., the reaction is warmed to -50° C. and stirred 5 minutes more. The mixture is then quenched with 1N HCl/ether. The product is extracted from 1N HCl with 3 portions of ether, and the ether layers are combined and washed with water. The resulting ether layer is dried (MgSO4), filtered, and concentrated in vacuo to give 2.14 g crude product. The product is flash chromatographed on silica gel using 10% EtOAc in hexane to give 0.97 g 2-t-butyl-4-(5-hexynoyl)-6-methylphenol. Crystallization from hexane gives crystals, mp 63°-64° C. the reaction is warmed to -50° C. stirred 5 minutes more The mixture is then quenched with 1N HCl/ether The product is extracted from 1N HCl with 3 portions of ether washed with water The resulting ether layer is dried (MgSO4) filtered concentrated in vacuo to give 2.14 g crude product chromatographed on silica gel using 10% EtOAc in hexane

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 2-allyl-6-t-butylphenol (0.57 g; 3 mmol) in dry CH2Cl2 (12 ml) is cooled to -78° C., and 5-hexynoyl chloride (0.43 g; 3.3 mmol) is added via syringe, followed by SnCl4 (0.375 ml) added dropwise via syringe, with stirring under Argon. After 30 min the reaction is allowed to warm to 0° C. and is stirred at that temperature for 5 min; it is then quenched with ca 1 ml of 3N HCl. The reaction is poured into 100 ml water and extracted with 3×50 ml portions of ether. The combined ether layers are washed with 150 ml portions of water until the aqueous layer is neutral (pH test). The ether layer is dried (MgSO4), filtered, and concentrated in vacuo to give crude product, which is chromatographed with 20:1 hexane/EtOAc, giving 0.64 g 2-allyl-4-(5-hexynoyl)-6-t-butylphenol (77% yield). The product is recrystallized from hexane at 0° C. to give crystals melting at 62°-63° C. added dropwise via syringe is stirred at that temperature for 5 min it is then quenched with ca 1 ml of 3N HCl The reaction is poured into 100 ml water extracted with 3×50 ml portions of ether The combined ether layers are washed with 150 ml portions of water until the aqueous layer The ether layer is dried (MgSO4) filtered concentrated in vacuo to give crude product, which is chromatographed with 20:1 hexane/EtOAc

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 2-allyl-6-t-butylphenol (0.57 g; 3 mmol) in dry CH2Cl2 (12 ml) is cooled to -78° C., and 5-hexynoyl chloride (0.43 g; 3.3 mmol) is added via syringe, followed by SnCl4 (0.375 ml) added dropwise via syringe, with stirring under Argon. After 30 min the reaction is allowed to warm to 0° C. and is stirred at that temperature for 5 min; it is then quenched with ca 1 ml of 3N HCl. The reaction is poured into 100 ml water and extracted with 3×50 ml portions of ether. The combined ether layers are washed with 150 ml portions of water until the aqueous layer is neutral (pH test). The ether layer is dried (MgSO4), filtered, and concentrated in vacuo to give crude product, which is chromatographed with 20:1 hexane/EtOAc, giving 0.64 g 2-allyl-4-(5-hexynoyl)-6-t-butylphenol (77% yield). The product is recrystallized from hexane at 0° C. to give crystals melting at 62°-63° C. added dropwise via syringe is stirred at that temperature for 5 min it is then quenched with ca 1 ml of 3N HCl The reaction is poured into 100 ml water extracted with 3×50 ml portions of ether The combined ether layers are washed with 150 ml portions of water until the aqueous layer The ether layer is dried (MgSO4) filtered concentrated in vacuo to give crude product, which is chromatographed with 20:1 hexane/EtOAc

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 2-allyl-6-t-butylphenol (0.57 g; 3 mmol) in dry CH2Cl2 (12 ml) is cooled to -78° C., and 5-hexynoyl chloride (0.43 g; 3.3 mmol) is added via syringe, followed by SnCl4 (0.375 ml) added dropwise via syringe, with stirring under Argon. After 30 min the reaction is allowed to warm to 0° C. and is stirred at that temperature for 5 min; it is then quenched with ca 1 ml of 3N HCl. The reaction is poured into 100 ml water and extracted with 3×50 ml portions of ether. The combined ether layers are washed with 150 ml portions of water until the aqueous layer is neutral (pH test). The ether layer is dried (MgSO4), filtered, and concentrated in vacuo to give crude product, which is chromatographed with 20:1 hexane/EtOAc, giving 0.64 g 2-allyl-4-(5-hexynoyl)-6-t-butylphenol (77% yield). The product is recrystallized from hexane at 0° C. to give crystals melting at 62°-63° C. added dropwise via syringe is stirred at that temperature for 5 min it is then quenched with ca 1 ml of 3N HCl The reaction is poured into 100 ml water extracted with 3×50 ml portions of ether The combined ether layers are washed with 150 ml portions of water until the aqueous layer The ether layer is dried (MgSO4) filtered concentrated in vacuo to give crude product, which is chromatographed with 20:1 hexane/EtOAc

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 2-tert-butyl-6-methylphenol (1.2 g, 7.3 mmol) in methylene chloride (28 ml, 1.1 equiv.), stirred under argon at -78° C., is added 5-hexynoyl chloride (1.0 g) followed by tin tetrachloride (0.93 mL, 1.1 equiv.). After stirring 30 minutes at -78° C., the reaction is warmed to -50° C. and stirred 5 minutes more. The mixture is then quenched with 1N HCl/ether. The product is extracted from 1N HCl with 3 portions of ether, and the ether layers are combined and washed with water. The resulting ether layer is dried (MgSO4), filtered, and concentrated in vacuo to give 2.14 g crude product. The product is flash chromatographed on silica gel using 10% EtOAc in hexane to give 0.97 g 2-t-butyl-4-(5-hexynoyl)-6-methylphenol. Crystallization from hexane gives crystals, mp 63°-64° C. the reaction is warmed to -50° C. stirred 5 minutes more The mixture is then quenched with 1N HCl/ether The product is extracted from 1N HCl with 3 portions of ether washed with water The resulting ether layer is dried (MgSO4) filtered concentrated in vacuo to give 2.14 g crude product chromatographed on silica gel using 10% EtOAc in hexane

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-amine (251 mg, 0.81 mmol) in dichloromethane (10 mL) was added triethylamine (0.22 mL, 1.62 mmol), hex-5-ynoyl chloride (211 mg, 1.62 mmol). The reaction mixture was stirred for 5 hours at room temperature, concentrated in vacuo, and then purified by silica gel chromatography to yield to N-{6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}hex-5-ynamide [200 mg; 95% of purity; 58% of theory; HPLC/MS: m/z=404 (M+H); log P(HCOOH)=2.98]. concentrated in vacuo purified by silica gel chromatography

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 2-allyl-6-t-butylphenol (0.57 g; 3 mmol) in dry CH2Cl2 (12 ml) is cooled to -78° C., and 5-hexynoyl chloride (0.43 g; 3.3 mmol) is added via syringe, followed by SnCl4 (0.375 ml) added dropwise via syringe, with stirring under Argon. After 30 min the reaction is allowed to warm to 0° C. and is stirred at that temperature for 5 min; it is then quenched with ca 1 ml of 3N HCl. The reaction is poured into 100 ml water and extracted with 3×50 ml portions of ether. The combined ether layers are washed with 150 ml portions of water until the aqueous layer is neutral (pH test). The ether layer is dried (MgSO4), filtered, and concentrated in vacuo to give crude product, which is chromatographed with 20:1 hexane/EtOAc, giving 0.64 g 2-allyl-4-(5-hexynoyl)-6-t-butylphenol (77% yield). The product is recrystallized from hexane at 0° C. to give crystals melting at 62°-63° C. added dropwise via syringe is stirred at that temperature for 5 min it is then quenched with ca 1 ml of 3N HCl The reaction is poured into 100 ml water extracted with 3×50 ml portions of ether The combined ether layers are washed with 150 ml portions of water until the aqueous layer The ether layer is dried (MgSO4) filtered concentrated in vacuo to give crude product, which is chromatographed with 20:1 hexane/EtOAc

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 2-allyl-6-t-butylphenol (0.57 g; 3 mmol) in dry CH2Cl2 (12 ml) is cooled to -78° C., and 5-hexynoyl chloride (0.43 g; 3.3 mmol) is added via syringe, followed by SnCl4 (0.375 ml) added dropwise via syringe, with stirring under Argon. After 30 min the reaction is allowed to warm to 0° C. and is stirred at that temperature for 5 min; it is then quenched with ca 1 ml of 3N HCl. The reaction is poured into 100 ml water and extracted with 3×50 ml portions of ether. The combined ether layers are washed with 150 ml portions of water until the aqueous layer is neutral (pH test). The ether layer is dried (MgSO4), filtered, and concentrated in vacuo to give crude product, which is chromatographed with 20:1 hexane/EtOAc, giving 0.64 g 2-allyl-4-(5-hexynoyl)-6-t-butylphenol (77% yield). The product is recrystallized from hexane at 0° C. to give crystals melting at 62°-63° C. added dropwise via syringe is stirred at that temperature for 5 min it is then quenched with ca 1 ml of 3N HCl The reaction is poured into 100 ml water extracted with 3×50 ml portions of ether The combined ether layers are washed with 150 ml portions of water until the aqueous layer The ether layer is dried (MgSO4) filtered concentrated in vacuo to give crude product, which is chromatographed with 20:1 hexane/EtOAc

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 2-tert-butyl-6-methylphenol (1.2 g, 7.3 mmol) in methylene chloride (28 ml, 1.1 equiv.), stirred under argon at -78° C., is added 5-hexynoyl chloride (1.0 g) followed by tin tetrachloride (0.93 mL, 1.1 equiv.). After stirring 30 minutes at -78° C., the reaction is warmed to -50° C. and stirred 5 minutes more. The mixture is then quenched with 1N HCl/ether. The product is extracted from 1N HCl with 3 portions of ether, and the ether layers are combined and washed with water. The resulting ether layer is dried (MgSO4), filtered, and concentrated in vacuo to give 2.14 g crude product. The product is flash chromatographed on silica gel using 10% EtOAc in hexane to give 0.97 g 2-t-butyl-4-(5-hexynoyl)-6-methylphenol. Crystallization from hexane gives crystals, mp 63°-64° C. the reaction is warmed to -50° C. stirred 5 minutes more The mixture is then quenched with 1N HCl/ether The product is extracted from 1N HCl with 3 portions of ether washed with water The resulting ether layer is dried (MgSO4) filtered concentrated in vacuo to give 2.14 g crude product chromatographed on silica gel using 10% EtOAc in hexane