3,4-dibromobutanenitrile

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

実験手順: The starting material is prepared as follows: To the solution of 1,134 g of bromine in 1,400 ml of ethyl acetate 472 g of allyl cyanide are added dropwise while stirring for 90 minutes at -10°-0°. The resulting solution of 3,4-dibromobutyronitrile is added all at once to the solution prepared from 705 g of catechol and 1,987 g of anhydrous potassium carbonate in 5,000 ml of refluxing ethyl acetate, while stirring at 35° under nitrogen. The mixture is refluxed for 4 hours and stirred overnight at room temperature. It is filtered, the residue washed with 2,000 ml of ethyl acetate, the filtrate evaporated, the residue distilled and the fraction boiling at 138°/1.4-131°/1.1 mm Hg collected, to yield the 1,4-benzodioxan-2-yl-acetonitrile. The starting material is prepared while stirring at 35° under nitrogen The mixture is refluxed for 4 hours stirred overnight at room temperature It is filtered the residue washed with 2,000 ml of ethyl acetate the filtrate evaporated the residue distilled the fraction boiling at 138°/1.4-131°/1.1 mm Hg collected

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

実験手順: To the refluxing solution of 75 g of 2-hydroxythiophenol [J. Pharm. Sci. 61, 2 (1972)] in 660 ml of acetone is added 42 g of potassium carbonate, followed by the dropwise addition of the solution of 33.5 g of 3,4-dibromobutyronitrile in 50 ml of acetone while stirring. After 30 minutes refluxing, a second, third, and fourth addition of 42 g potassium carbonate and 33.5 g of 3,4-dibromobutyronitrile is made. The whole mixture is refluxed for 20 hours, cooled and filtered. The filtrate is evaporated and the residue distilled in a bulb to bulb apparatus at 185° and 0.5 mmHg, to yield the 2-(1,4-benzoxathian-2-yl)-acetonitrile. After 30 minutes refluxing The whole mixture is refluxed for 20 hours cooled filtered The filtrate is evaporated the residue distilled in a bulb to bulb apparatus at 185°

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

実験手順: The starting material is prepared as follows: To the stirred, refluxing solution of 21 g of 2-hydroxy-thiophenol in 290 ml of acetone is added dropwise 12.5 g of 3,4-dibromo-butyronitrile along with small portions of 15.8 g of anhydrous potassium carbonate. After 30 minutes, the double addition procedure with said amounts of dibromo compound and potassium carbonate is repeated, and after a further 30 minutes said procedure is repeated a third time. The mixture is then refluxed for 20 hours, cooled, filtered, the residual salts washed with acetone, and the filtrate evaporated. The residue is distilled (bulb to bulb), and the fraction boiling at 185°/0.5 mm Hg collected, to yield the 2-(1,4-benzoxathian-2-yl)-acetonitrile. The starting material is prepared the double addition procedure after a further 30 minutes said The mixture is then refluxed for 20 hours cooled filtered the residual salts washed with acetone the filtrate evaporated The residue is distilled (bulb to bulb) the fraction boiling at 185°/0.5 mm Hg collected

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

実験手順: The starting material is prepared as follows: To the stirred, refluxing solution of 21 g of 2-hydroxy-thiophenol in 290 ml of acetone is added dropwise 12.5 g of 3,4-dibromo-butyronitrile along with small portions of 15.8 g of anhydrous potassium carbonate. After 30 minutes, the double addition procedure with said amounts of dibromo compound and potassium carbonate is repeated, and after a further 30 minutes said procedure is repeated a third time. The mixture is then refluxed for 20 hours, cooled, filtered, the residual salts washed with acetone, and the filtrate evaporated. The residue is distilled (bulb to bulb), and the fraction boiling at 185°/0.5 mm Hg collected, to yield the 2-(1,4-benzoxathian-2-yl)-acetonitrile. The starting material is prepared the double addition procedure after a further 30 minutes said The mixture is then refluxed for 20 hours cooled filtered the residual salts washed with acetone the filtrate evaporated The residue is distilled (bulb to bulb) the fraction boiling at 185°/0.5 mm Hg collected

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

実験手順: The starting material is prepared as follows: To the stirred, refluxing solution of 21 g of 2-hydroxy-thiophenol in 290 ml of acetone is added dropwise 12.5 g of 3,4-dibromo-butyronitrile along with small portions of 15.8 g of anhydrous potassium carbonate. After 30 minutes, the double addition procedure with said amounts of dibromo compound and potassium carbonate is repeated, and after a further 30 minutes said procedure is repeated a third time. The mixture is then refluxed for 20 hours, cooled, filtered, the residual salts washed with acetone, and the filtrate evaporated. The residue is distilled (bulb to bulb), and the fraction boiling at 185°/0.5 mm Hg collected, to yield the 2-(1,4-benzoxathian-2-yl)-acetonitrile. The starting material is prepared the double addition procedure after a further 30 minutes said The mixture is then refluxed for 20 hours cooled filtered the residual salts washed with acetone the filtrate evaporated The residue is distilled (bulb to bulb) the fraction boiling at 185°/0.5 mm Hg collected

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

実験手順: The starting material is prepared as follows: To the stirred, refluxing solution of 21 g of 2-hydroxy-thiophenol in 290 ml of acetone is added dropwise 12.5 g of 3,4-dibromo-butyronitrile along with small portions of 15.8 g of anhydrous potassium carbonate. After 30 minutes, the double addition procedure with said amounts of dibromo compound and potassium carbonate is repeated, and after a further 30 minutes said procedure is repeated a third time. The mixture is then refluxed for 20 hours, cooled, filtered, and the residual salts washed with acetone, and the filtrate evaporated. The residue is distilled (bulb to bulb), and the fraction boiling at 185°/0.5 mm Hg collected, to yield the 2-(1,4-benzoxathian-2-yl)-acetonitrile. The starting material is prepared the double addition procedure after a further 30 minutes said The mixture is then refluxed for 20 hours cooled filtered the residual salts washed with acetone the filtrate evaporated The residue is distilled (bulb to bulb) the fraction boiling at 185°/0.5 mm Hg collected

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

実験手順: The starting material is prepared as follows: To the solution of 1,134 g of bromine in 1,400 ml of ethyl acetate 472 g of allyl cyanide are added dropwise while stirring for 90 minutes at -10°-0°. The resulting solution of 3,4-dibromobutyronitrile is added all at once to the solution prepared from 705 g of catechol and 1,987 g of anhydrous potassium carbonate in 5,000 ml of refluxing ethyl acetate, while stirring at 35° under nitrogen. The mixture is refluxed for 4 hours and stirred overnight at room temperature. It is filtered, the residue washed with 2,000 ml of ethyl acetate, the filtrate evaporated, the residue distilled and the fraction boiling at 138°/1.4-131°/1.1 mm Hg collected, to yield the 1,4-benzodioxan-2-yl-acetonitrile. The starting material is prepared while stirring at 35° under nitrogen The mixture is refluxed for 4 hours stirred overnight at room temperature It is filtered the residue washed with 2,000 ml of ethyl acetate the filtrate evaporated the residue distilled the fraction boiling at 138°/1.4-131°/1.1 mm Hg collected

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

実験手順: To the refluxing solution of 75 g of 2-hydroxythiophenol [J. Pharm. Sci. 61, 2 (1972)] in 660 ml of acetone is added 42 g of potassium carbonate, followed by the dropwise addition of the solution of 33.5 g of 3,4-dibromobutyronitrile in 50 ml of acetone while stirring. After 30 minutes refluxing, a second, third, and fourth addition of 42 g potassium carbonate and 33.5 g of 3,4-dibromobutyronitrile is made. The whole mixture is refluxed for 20 hours, cooled and filtered. The filtrate is evaporated and the residue distilled in a bulb to bulb apparatus at 185° and 0.5 mmHg, to yield the 2-(1,4-benzoxathian-2-yl)-acetonitrile. After 30 minutes refluxing The whole mixture is refluxed for 20 hours cooled filtered The filtrate is evaporated the residue distilled in a bulb to bulb apparatus at 185°

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

実験手順: The starting material is prepared as follows: To the stirred, refluxing solution of 21 g of 2-hydroxy-thiophenol in 290 ml of acetone is added dropwise 12.5 g of 3,4-dibromo-butyronitrile along with small portions of 15.8 g of anhydrous potassium carbonate. After 30 minutes, the double addition procedure with said amounts of dibromo compound and potassium carbonate is repeated, and after a further 30 minutes said procedure is repeated a third time. The mixture is then refluxed for 20 hours, cooled, filtered, the residual salts washed with acetone, and the filtrate evaporated. The residue is distilled (bulb to bulb), and the fraction boiling at 185°/0.5 mm Hg collected, to yield the 2-(1,4-benzoxathian-2-yl)-acetonitrile. The starting material is prepared the double addition procedure after a further 30 minutes said The mixture is then refluxed for 20 hours cooled filtered the residual salts washed with acetone the filtrate evaporated The residue is distilled (bulb to bulb) the fraction boiling at 185°/0.5 mm Hg collected