2-ethynylbenzaldehyde

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:127.800003051757811; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The protected ethynyl benzaldehyde was prepared as follows. In a 50 ml. two-necked round bottom flask equipped with a magnetic stirring bar, argon inlet, and a reflux condenser was placed 1.62 g. (0.0087 mol.) of bromobenzaldehyde and 28.3 ml. dry pyridine. The pyridine had been dried over sodium hydroxide pellets and distilled. The flask was purged with argon while stirring and 1.58 g. (0.0084 mol.) of the copper acetylide salt was added during the argon flush. Upon addition of the copper acetylide salt, the reaction mixture became reddish amber in color. The contents were heated in a wax bath at 127.8° C. for eighteen hours. Caution was taken to prevent particles from burning on the sides of the flask by keeping the wax bath below the reaction mixture's volume line. As the reaction progressed, the color of solution turned from a reddish to brownish amber and a darkly colored precipitate had formed. Upon completion of the reaction the solution was cooled and quenched with 85 ml. of deionized water. The precipitate was isolated by suction filtration and washed with approximately 70 ml. of deionized water. Immediately after the wash solution hit the floor of the receiving flask, a tan in color precipitate came out of solution. Upon further addition of wash solution, the precipitate became lighter in color and brown oil droplets lined the bottom of the erlenmeyer flask. What remained on the filter paper was a brownish black precipitate which was subsequently washed with 120 ml. of ether. The ethereal wash solution became tan in color. The combined ethereal and aqueous wash solutions were transferred to a 1000 ml. separatory funnel for separation. After mixing of the ethereal layer and the aqueous layer, the ether layer became darker in color while the aqueous layer took on a light yellowish green color. Two additional extractions with ether, 40 ml. each, were done on the aqueous layer. The combined ether extracts were washed successively with 50 ml. each of 0.1 N. hydrochloric acid, 5% sodium bicarbonate, and deionized water, and dried over magnesium sulfate. The dried ethereal solution was placed in a rotary evaporate at 30° C.; however, not all the solvent evaporated. What remained in the round bottom flask was a brownish amber liquid with an odor characteristic of pyridine. This was put under vacuum (3 mm.) at 75° C. Only a few milliliters of solvent were pulled over; the product remained in solution. two-necked round bottom flask equipped with a magnetic stirring bar, argon inlet, and a reflux condenser The pyridine had been dried over sodium hydroxide pellets distilled The flask was purged with argon flush Upon addition of the copper acetylide salt a darkly colored precipitate had formed Upon completion of the reaction the solution was cooled quenched with 85 ml The precipitate was isolated by suction filtration washed with approximately 70 ml Upon further addition of wash solution was subsequently washed with 120 ml separatory funnel for separation After mixing of the ethereal layer Two additional extractions with ether, 40 ml The combined ether extracts were washed successively with 50 ml dried over magnesium sulfate a rotary evaporate at 30° C. however, not all the solvent evaporated This was put under vacuum (3 mm.) at 75° C

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 2-ethynylbenzaldehyde (200 mg, 1.54 mmol) and benzyl azide (0.38 mL, 3.0 mmol) in 2.0 mL of N,N-dimethylformamide was stirred at 80° C. overnight. The reaction mixture was diluted with water, and the solution was extracted with a 5:1 solution (12 mL) of ethyl acetate and hexane. The extract was washed with water, brine, and dried over MgSO4. After filtration, the filtrate was concentrated in vacuo, and the residue was purified with silica gel column chromatography (hexane/ethyl acetate=80/20 to 60/40) to obtain 2-(1-benzyl-1H-1,2,3-triazol-4-yl)benzaldehyde (259 mg, 65%) and 2-(1-benzyl-1H-1,2,3-triazol-5-yl)benzaldehyde (118 mg, 30%). the solution was extracted with a 5:1 solution (12 mL) of ethyl acetate and hexane The extract was washed with water, brine dried over MgSO4 After filtration the filtrate was concentrated in vacuo the residue was purified with silica gel column chromatography (hexane/ethyl acetate=80/20 to 60/40)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 2-ethynylbenzaldehyde (200 mg, 1.54 mmol) and benzyl azide (0.38 mL, 3.0 mmol) in 2.0 mL of N,N-dimethylformamide was stirred at 80° C. overnight. The reaction mixture was diluted with water, and the solution was extracted with a 5:1 solution (12 mL) of ethyl acetate and hexane. The extract was washed with water, brine, and dried over MgSO4. After filtration, the filtrate was concentrated in vacuo, and the residue was purified with silica gel column chromatography (hexane/ethyl acetate=80/20 to 60/40) to obtain 2-(1-benzyl-1H-1,2,3-triazol-4-yl)benzaldehyde (259 mg, 65%) and 2-(1-benzyl-1H-1,2,3-triazol-5-yl)benzaldehyde (118 mg, 30%). the solution was extracted with a 5:1 solution (12 mL) of ethyl acetate and hexane The extract was washed with water, brine dried over MgSO4 After filtration the filtrate was concentrated in vacuo the residue was purified with silica gel column chromatography (hexane/ethyl acetate=80/20 to 60/40)

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 4-bromo-N,N-dimethylbenzenesulfonamide (610 mg, 2.31 mmol) bis(triphenylphosphine)palladium(II) chloride (Pd(PPh3)2Cl2) (33 mg, 0.05 mmol), copper (I) iodide (5 mg, 0.03 mmol) and triethylamine (3 mL) was degassed with argon. To the above mixture was added a degassed solution of 2-ethynyl-benzaldehyde (300 mg, 2.31 mmol) in acetonitrile (3 mL). The resulting mixture was heated at 80° C. for 3 hours under argon, and then cooled to room temperature, treated with ethyl acetate, and then washed with water. The organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. Flash chromatography (RediSep® Flash column, 230-400 mesh, 5-40% ethyl acetate in hexane) gave 4-(2-formyl-phenylethynyl)-N,N-dimethyl-benzenesulfonamide (454 mg, 63%) as a brown oil. MS (ESI+) cald. for C17H15NO3S [(M+H)+] 313, obsd. 314. was degassed with argon cooled to room temperature washed with water The organic layer was dried over anhydrous sodium sulfate filtered concentrated in vacuo

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 2-trimethylsilanylethynyl-benzaldehyde (6 g, 29.70 mmol) in N,N-dimethylformamide (10 mL) was added potassium fluoride (1 g, 17.2 mmol). The reaction mixture was stirred at room temperature for 30 minutes. The resulting solution was poured into water, and then extracted with dichloromethane. The collected organic layers were dried over magnesium sulfate, filtered, and concentrated in vacuo. Flash chromatography (RediSep® Flash column, 230-400 mesh, 0-25% ethyl acetate in hexane) gave 2-ethynyl-benzaldehyde (2.8 g, 73%) as a white solid. MS (ESI+) cald for C9H6O [(M+H)+] 130, obsd. 131. extracted with dichloromethane The collected organic layers were dried over magnesium sulfate filtered concentrated in vacuo

Conditions: temp:127.800003051757811; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The protected ethynyl benzaldehyde was prepared as follows. In a 50 ml. two-necked round bottom flask equipped with a magnetic stirring bar, argon inlet, and a reflux condenser was placed 1.62 g. (0.0087 mol.) of bromobenzaldehyde and 28.3 ml. dry pyridine. The pyridine had been dried over sodium hydroxide pellets and distilled. The flask was purged with argon while stirring and 1.58 g. (0.0084 mol.) of the copper acetylide salt was added during the argon flush. Upon addition of the copper acetylide salt, the reaction mixture became reddish amber in color. The contents were heated in a wax bath at 127.8° C. for eighteen hours. Caution was taken to prevent particles from burning on the sides of the flask by keeping the wax bath below the reaction mixture's volume line. As the reaction progressed, the color of solution turned from a reddish to brownish amber and a darkly colored precipitate had formed. Upon completion of the reaction the solution was cooled and quenched with 85 ml. of deionized water. The precipitate was isolated by suction filtration and washed with approximately 70 ml. of deionized water. Immediately after the wash solution hit the floor of the receiving flask, a tan in color precipitate came out of solution. Upon further addition of wash solution, the precipitate became lighter in color and brown oil droplets lined the bottom of the erlenmeyer flask. What remained on the filter paper was a brownish black precipitate which was subsequently washed with 120 ml. of ether. The ethereal wash solution became tan in color. The combined ethereal and aqueous wash solutions were transferred to a 1000 ml. separatory funnel for separation. After mixing of the ethereal layer and the aqueous layer, the ether layer became darker in color while the aqueous layer took on a light yellowish green color. Two additional extractions with ether, 40 ml. each, were done on the aqueous layer. The combined ether extracts were washed successively with 50 ml. each of 0.1 N. hydrochloric acid, 5% sodium bicarbonate, and deionized water, and dried over magnesium sulfate. The dried ethereal solution was placed in a rotary evaporate at 30° C.; however, not all the solvent evaporated. What remained in the round bottom flask was a brownish amber liquid with an odor characteristic of pyridine. This was put under vacuum (3 mm.) at 75° C. Only a few milliliters of solvent were pulled over; the product remained in solution. two-necked round bottom flask equipped with a magnetic stirring bar, argon inlet, and a reflux condenser The pyridine had been dried over sodium hydroxide pellets distilled The flask was purged with argon flush Upon addition of the copper acetylide salt a darkly colored precipitate had formed Upon completion of the reaction the solution was cooled quenched with 85 ml The precipitate was isolated by suction filtration washed with approximately 70 ml Upon further addition of wash solution was subsequently washed with 120 ml separatory funnel for separation After mixing of the ethereal layer Two additional extractions with ether, 40 ml The combined ether extracts were washed successively with 50 ml dried over magnesium sulfate a rotary evaporate at 30° C. however, not all the solvent evaporated This was put under vacuum (3 mm.) at 75° C

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 2-ethynylbenzaldehyde (200 mg, 1.54 mmol) and benzyl azide (0.38 mL, 3.0 mmol) in 2.0 mL of N,N-dimethylformamide was stirred at 80° C. overnight. The reaction mixture was diluted with water, and the solution was extracted with a 5:1 solution (12 mL) of ethyl acetate and hexane. The extract was washed with water, brine, and dried over MgSO4. After filtration, the filtrate was concentrated in vacuo, and the residue was purified with silica gel column chromatography (hexane/ethyl acetate=80/20 to 60/40) to obtain 2-(1-benzyl-1H-1,2,3-triazol-4-yl)benzaldehyde (259 mg, 65%) and 2-(1-benzyl-1H-1,2,3-triazol-5-yl)benzaldehyde (118 mg, 30%). the solution was extracted with a 5:1 solution (12 mL) of ethyl acetate and hexane The extract was washed with water, brine dried over MgSO4 After filtration the filtrate was concentrated in vacuo the residue was purified with silica gel column chromatography (hexane/ethyl acetate=80/20 to 60/40)