bicyclo[4.2.0]octa-1,3,5-triene-7-carbonitrile

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

Procedure: A 3-liter, three-necked flask equipped with a dry ice condenser, mechanical stirrer and Claisen adapter fitted with an ammonia gas inlet and nitrogen inlet is rinsed with acetone, dried in an oven at 125° C., and heated with an air gun while flushing with nitrogen. The apparatus is cooled in a dry ice-acetone bath and the condenser is filled with a dry ice-acetone mixture. Ammonia gas flow is initiated and 600 ml is condensed out. The ammonia inlet tube is replaced by a stopper, and 0.4 g of powdered iron (III) nitrate is added. Sodium metal, 51.52 g (2.24 moles) is added in small portions over 1 hour. After all the sodium is added, the dry ice bath is removed and cooling is left to the dry ice condenser. Complete conversion of the sodium/ammonia solution to sodamide is indicated by a color change from deep blue to gray. Next, 92.82 g (0.56 mole) of 3-(o-chlorophenyl)propionitrile is added over a period of 10 minutes. The last traces of the nitrile are washed into the flask with small amounts of anhydrous ethyl ether. The dark green reaction mixture is stirred vigorously for 3 hours and then is treated with 134.4 g (1.68 moles) of solid ammonium nitrate. The ammonia is allowed to evaporate overnight at room temperature. Water (420 ml) is cautiously added to the residue. The organic layer is taken up in two 224-ml portions of chloroform, and the solutions are combined and washed twice with 140 ml of aqueous 5 percent hydrochloric acid and once with 140 ml of water. The chloroform solution is dried over anhydrous magnesium sulfate, filtered, and evaporated on a rotary evaporator. The residual liquid is distilled under reduced pressure through an insulated 12-inch Vigreux column. The product is collected at 59° C.-69° C./0.2 mm Hg. The infrared, 'H and 13C nuclear magnetic resonance are run to identify the product. The yield is 50 percent. A 3-liter, three-necked flask equipped with a dry ice condenser, mechanical stirrer Claisen adapter fitted with an ammonia gas inlet and nitrogen inlet is rinsed with acetone dried in an oven at 125° C. heated with an air gun while flushing with nitrogen The apparatus is cooled in a dry ice-acetone bath the condenser is filled with a dry ice-acetone mixture condensed out is added the dry ice bath is removed cooling is left to the dry ice condenser The last traces of the nitrile are washed into the flask with small amounts of anhydrous ethyl ether to evaporate overnight at room temperature Water (420 ml) is cautiously added to the residue washed twice with 140 ml of aqueous 5 percent hydrochloric acid and once with 140 ml of water The chloroform solution is dried over anhydrous magnesium sulfate filtered evaporated on a rotary evaporator The residual liquid is distilled under reduced pressure through an insulated 12-inch Vigreux column The product is collected at 59° C.-69° C./0.2 mm Hg

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

Procedure: A 3-liter, three-necked flask equipped with a dry ice condenser, mechanical stirrer and Claisen adapter fitted with an ammonia gas inlet and nitrogen inlet is rinsed with acetone, dried in an oven at 125° C., and heated with an air gun while flushing with nitrogen. The apparatus is cooled in a dry ice-acetone bath and the condenser is filled with a dry ice-acetone mixture. Ammonia gas flow is initiated and 600 ml is condensed out. The ammonia inlet tube is replaced by a stopper, and 0.4 g of powdered iron (III) nitrate is added. Sodium metal, 51.52 g (2.24 moles) is added in small portions over 1 hour. After all the sodium is added, the dry ice bath is removed and cooling is left to the dry ice condenser. Complete conversion of the sodium/ammonia solution to sodamide is indicated by a color change from deep blue to gray. Next, 92.82 g (0.56 mole) of o-chlorocinnamonitrile is added over a period of 10 minutes. The last traces of the nitrile are washed into the flask with small amounts of anhydrous ethyl ether. The dark green reaction mixture is stirred vigorously for 3 hours and then is treated with 134.4 g (1.68 moles) of solid ammonium nitrate. The ammonia is allowed to evaporate overnight at room temperature. Water (420 ml) is cautiously added to the residue. The organic layer is taken up in two 224-ml portions of chloroform, and the solutions are combined and washed twice with 140 ml of aqueous 5 percent hydrochloric acid and once with 140 ml of water. The chloroform solution is dried over anhydrous magnesium sulfate, filtered, and evaporated on a rotary evaporator. The residual liquid is distilled under reduced pressure through an insulated 12-inch Vigreux column. The product is collected at 59° C.-69° C./0.2 mm Hg. The infrared, 'H and 13C nuclear magnetic resonance are run to identify the product. The yield is 50 percent. A 3-liter, three-necked flask equipped with a dry ice condenser, mechanical stirrer Claisen adapter fitted with an ammonia gas inlet and nitrogen inlet is rinsed with acetone dried in an oven at 125° C. heated with an air gun while flushing with nitrogen The apparatus is cooled in a dry ice-acetone bath the condenser is filled with a dry ice-acetone mixture condensed out is added the dry ice bath is removed cooling is left to the dry ice condenser The last traces of the nitrile are washed into the flask with small amounts of anhydrous ethyl ether to evaporate overnight at room temperature Water (420 ml) is cautiously added to the residue washed twice with 140 ml of aqueous 5 percent hydrochloric acid and once with 140 ml of water The chloroform solution is dried over anhydrous magnesium sulfate filtered evaporated on a rotary evaporator The residual liquid is distilled under reduced pressure through an insulated 12-inch Vigreux column The product is collected at 59° C.-69° C./0.2 mm Hg

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

Procedure: A 3-liter, three-necked flask equipped with a dry ice condenser, mechanical stirrer and Claisen adapter fitted with an ammonia gas inlet and nitrogen inlet is rinsed with acetone, dried in an oven at 125° C., and heated with an air gun while flushing with nitrogen. The apparatus is cooled in a dry ice-acetone bath and the condenser is filled with a dry ice-acetone mixture. Ammonia gas flow is initiated and 600 ml is condensed out. The ammonia inlet tube is replaced by a stopper, and 0.4 g of powdered iron (III) nitrate is added. Sodium metal, 51.52 g (2.24 moles) is added in small portions over 1 hour. After all the sodium is added, the dry ice bath is removed and cooling is left to the dry ice condenser. Complete conversion of the sodium/ammonia solution to sodamide is indicated by a color change from deep blue to gray. Next, 92.82 g (0.56 mole) of o-chlorocinnamonitrile is added over a period of 10 minutes. The last traces of the nitrile are washed into the flask with small amounts of anhydrous ethyl ether. The dark green reaction mixture is stirred vigorously for 3 hours and then is treated with 134.4 g (1.68 moles) of solid ammonium nitrate. The ammonia is allowed to evaporate overnight at room temperature. Water (420 ml) is cautiously added to the residue. The organic layer is taken up in two 224-ml portions of chloroform, and the solutions are combined and washed twice with 140 ml of aqueous 5 percent hydrochloric acid and once with 140 ml of water. The chloroform solution is dried over anhydrous magnesium sulfate, filtered, and evaporated on a rotary evaporator. The residual liquid is distilled under reduced pressure through an insulated 12-inch Vigreux column. The product is collected at 59° C.-69° C./0.2 mm Hg. The infrared, 'H and 13C nuclear magnetic resonance are run to identify the product. The yield is 50 percent. A 3-liter, three-necked flask equipped with a dry ice condenser, mechanical stirrer Claisen adapter fitted with an ammonia gas inlet and nitrogen inlet is rinsed with acetone dried in an oven at 125° C. heated with an air gun while flushing with nitrogen The apparatus is cooled in a dry ice-acetone bath the condenser is filled with a dry ice-acetone mixture condensed out is added the dry ice bath is removed cooling is left to the dry ice condenser The last traces of the nitrile are washed into the flask with small amounts of anhydrous ethyl ether to evaporate overnight at room temperature Water (420 ml) is cautiously added to the residue washed twice with 140 ml of aqueous 5 percent hydrochloric acid and once with 140 ml of water The chloroform solution is dried over anhydrous magnesium sulfate filtered evaporated on a rotary evaporator The residual liquid is distilled under reduced pressure through an insulated 12-inch Vigreux column The product is collected at 59° C.-69° C./0.2 mm Hg

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Whilst maintaining the temperature at -78° C., 69 ml of 1.6M butyllithium in n-hexane are added to a solution of 12.9 g of 1-cyanobenzocyclobutane in 200 ml of tetrahydrofuran. After stirring for half an hour at that temperature, 15.5 ml of cyclohexanone are added and the reaction mixture is brought back to room temperature. After stirring for 3 hours at room temperature, the reaction mixture is hydrolysed at -10° C. with water. After extraction with diethyl ether, the organic phase is washed with brine, dried over MgSO4 and concentrated in vacuo. The crystalline residue is recrystallised from isopropyl ether to yield 12.32 g of the desired product. are added is brought back to room temperature After extraction with diethyl ether the organic phase is washed with brine dried over MgSO4 concentrated in vacuo The crystalline residue is recrystallised from isopropyl ether

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

Procedure: A 3-liter, three-necked flask equipped with a dry ice condenser, mechanical stirrer and Claisen adapter fitted with an ammonia gas inlet and nitrogen inlet is rinsed with acetone, dried in an oven at 125° C., and heated with an air gun while flushing with nitrogen. The apparatus is cooled in a dry ice-acetone bath and the condenser is filled with a dry ice-acetone mixture. Ammonia gas flow is initiated and 600 ml is condensed out. The ammonia inlet tube is replaced by a stopper, and 0.4 g of powdered iron (III) nitrate is added. Sodium metal, 51.52 g (2.24 moles) is added in small portions over 1 hour. After all the sodium is added, the dry ice bath is removed and cooling is left to the dry ice condenser. Complete conversion of the sodium/ammonium solution to sodamide is indicated by a color change from deep blue to gray. Next, 92.82 g (0.56 mole) of 3-(o-chlorophenyl)propionitrile is added over a period of 10 minutes. The last traces of the nitrile are washed into the flask with small amounts of anhydrous ethyl ether. The dark green reaction mixture is stirred vigorously for 3 hours and then is treated with 134.4 g (1.68 moles) of solid ammonium nitrate. The ammonia is allowed to evaporate overnight at room temperature. Water (420 ml) is cautiously added to the residue. The organic layer is taken up in two 224-ml portions of chloroform, and the solutions are combined and washed twice with 140 ml of aqueous 5 percent hydrochloric acid and once with 140 ml of water. The chloroform solution is dried over anhydrous magnesium sulfate, filtered, and evaporated on a rotary evaporator. The residual liquid is distilled under reduced pressure through an insulated 12-inch Vigreux column. The product is collected at 59° C.-69° C./0.2 mm Hg. The infrared, 'H and 13C nuclear magnetic resonance are run to identify the product. The yield is 50 percent. A 3-liter, three-necked flask equipped with a dry ice condenser, mechanical stirrer Claisen adapter fitted with an ammonia gas inlet and nitrogen inlet is rinsed with acetone dried in an oven at 125° C. heated with an air gun while flushing with nitrogen The apparatus is cooled in a dry ice-acetone bath the condenser is filled with a dry ice-acetone mixture condensed out is added the dry ice bath is removed cooling is left to the dry ice condenser The last traces of the nitrile are washed into the flask with small amounts of anhydrous ethyl ether to evaporate overnight at room temperature Water (420 ml) is cautiously added to the residue washed twice with 140 ml of aqueous 5 percent hydrochloric acid and once with 140 ml of water The chloroform solution is dried over anhydrous magnesium sulfate filtered evaporated on a rotary evaporator The residual liquid is distilled under reduced pressure through an insulated 12-inch Vigreux column The product is collected at 59° C.-69° C./0.2 mm Hg

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

Procedure: A 3-liter, three-necked flask equipped with a dry ice condenser, mechanical stirrer and Claisen adapter fitted with an ammonia gas inlet and nitrogen inlet is rinsed with acetone, dried in an oven at 125° C., and heated with an air gun while flushing with nitrogen. The apparatus is cooled in a dry ice-acetone bath and the condenser is filled with a dry ice-acetone mixture. Ammonia gas flow is initiated and 600 ml is condensed out. The ammonia inlet tube is replaced by a stopper, and 0.4 g of powdered iron (III) nitrate is added. Sodium metal, 51.52 g (2.24 moles) is added in small portions over 1 hour. After all the sodium is added, the dry ice bath is removed and cooling is left to the dry ice condenser. Complete conversion of the sodium/ammonia solution to sodamide is indicated by a color change from deep blue to gray. Next, 92.82 g (0.56 mole) of 3-(o-chlorophenyl)propionitrile is added over a period of 10 minutes. The last traces of the nitrile are washed into the flask with small amounts of anhydrous ethyl ether. The dark green reaction mixture is stirred vigorously for 3 hours and then is treated with 134.4 g (1.68 moles) of solid ammonium nitrate. The ammonia is allowed to evaporate overnight at room temperature. Water (420 ml) is cautiously added to the residue. The organic layer is taken up in two 224-ml portions of chloroform, and the solutions are combined and washed twice with 140 ml of aqueous 5 percent hydrochloric acid and once with 140 ml of water. The chloroform solution is dried over anhydrous magnesium sulfate, filtered, and evaporated on a rotary evaporator. The residual liquid is distilled under reduced pressure through an insulated 12-inch Vigreux column. The product is collected at 59° C.-69° C./0.2 mm Hg. The infrared, 'H and 13C nuclear magnetic resonance are run to identify the product. The yield is 50 percent. A 3-liter, three-necked flask equipped with a dry ice condenser, mechanical stirrer Claisen adapter fitted with an ammonia gas inlet and nitrogen inlet is rinsed with acetone dried in an oven at 125° C. heated with an air gun while flushing with nitrogen The apparatus is cooled in a dry ice-acetone bath the condenser is filled with a dry ice-acetone mixture condensed out is added the dry ice bath is removed cooling is left to the dry ice condenser The last traces of the nitrile are washed into the flask with small amounts of anhydrous ethyl ether to evaporate overnight at room temperature Water (420 ml) is cautiously added to the residue washed twice with 140 ml of aqueous 5 percent hydrochloric acid and once with 140 ml of water The chloroform solution is dried over anhydrous magnesium sulfate filtered evaporated on a rotary evaporator The residual liquid is distilled under reduced pressure through an insulated 12-inch Vigreux column The product is collected at 59° C.-69° C./0.2 mm Hg

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

Procedure: A 3-liter, three-necked flask equipped with a dry ice condenser, mechanical stirrer and Claisen adapter fitted with an ammonia gas inlet and nitrogen inlet is rinsed with acetone, dried in an oven at 125° C., and heated with an air gun while flushing with nitrogen. The apparatus is cooled in a dry ice-acetone bath and the condenser is filled with a dry ice-acetone mixture. Ammonia gas flow is initiated and 600 ml is condensed out. The ammonia inlet tube is replaced by a stopper, and 0.4 g of powdered iron (III) nitrate is added. Sodium metal, 51.52 g (2.24 moles) is added in small portions over 1 hour. After all the sodium is added, the dry ice bath is removed and cooling is left to the dry ice condenser. Complete conversion of the sodium/ammonia solution to sodamide is indicated by a color change from deep blue to gray. Next, 92.82 g (0.56 mole) of o-chlorocinnamonitrile is added over a period of 10 minutes. The last traces of the nitrile are washed into the flask with small amounts of anhydrous ethyl ether. The dark green reaction mixture is stirred vigorously for 3 hours and then is treated with 134.4 g (1.68 moles) of solid ammonium nitrate. The ammonia is allowed to evaporate overnight at room temperature. Water (420 ml) is cautiously added to the residue. The organic layer is taken up in two 224-ml portions of chloroform, and the solutions are combined and washed twice with 140 ml of aqueous 5 percent hydrochloric acid and once with 140 ml of water. The chloroform solution is dried over anhydrous magnesium sulfate, filtered, and evaporated on a rotary evaporator. The residual liquid is distilled under reduced pressure through an insulated 12-inch Vigreux column. The product is collected at 59° C.-69° C./0.2 mm Hg. The infrared, 'H and 13C nuclear magnetic resonance are run to identify the product. The yield is 50 percent. A 3-liter, three-necked flask equipped with a dry ice condenser, mechanical stirrer Claisen adapter fitted with an ammonia gas inlet and nitrogen inlet is rinsed with acetone dried in an oven at 125° C. heated with an air gun while flushing with nitrogen The apparatus is cooled in a dry ice-acetone bath the condenser is filled with a dry ice-acetone mixture condensed out is added the dry ice bath is removed cooling is left to the dry ice condenser The last traces of the nitrile are washed into the flask with small amounts of anhydrous ethyl ether to evaporate overnight at room temperature Water (420 ml) is cautiously added to the residue washed twice with 140 ml of aqueous 5 percent hydrochloric acid and once with 140 ml of water The chloroform solution is dried over anhydrous magnesium sulfate filtered evaporated on a rotary evaporator The residual liquid is distilled under reduced pressure through an insulated 12-inch Vigreux column The product is collected at 59° C.-69° C./0.2 mm Hg