1-chloro-4-prop-2-ynylbenzene

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

Procedure: Dissolve 150.6 g (1.00 mole) of 1-chloro-4-(2-propynyl)benzene in 600 ml of anhydrous ether under N2 atmosphere with stirring at dry ice/acetone temperature. Add dropwise a solution of 400 ml of n-butyllithium (2.5M in hexane) (1.00 mole). Stir for an additional 30 minutes after completion of addition. Add 31 g (1.00 mole) of paraformaldehyde. Stir the mixture at dry ice/acetone temperature for 1 hour, and allow to warm to room temperature. Follow the progress of the reaction by thin-layer chromatography on silica gel (methylene chloride). At the completion of the reaction, add 400 ml of saturated aqueous sodium chloride, separate layers, and extract aqueous layer with ether (2×100 ml). Wash the combined ether solutions with water, dry over magnesium sulfate and evaporate. Triturate the oil residue with petroleum ether to provide the title compound. after completion of addition the progress of the reaction by thin-layer chromatography on silica gel (methylene chloride) At the completion of the reaction separate layers extract aqueous layer with ether (2×100 ml) Wash the combined ether solutions with water dry over magnesium sulfate evaporate Triturate the oil residue with petroleum ether

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

Procedure: Dissolve 150.6 g (1.00 mole) of 1-chloro-4-(2-propynyl)benzene in 600 ml of anhydrous ether under N2 atmosphere with stirring at dry ice/acetone temperature. Add dropwise a solution of 400 ml of n-butyllithium (2.5M in hexane) (1.00 mole). Stir for an additional 30 minutes after completion of addition. Add 31 g (1.00 mole) of paraformaldehyde. Stir the mixture at dry ice/acetone temperature for 1 hour, and allow to warm to room temperature. Follow the progress of the reaction by thin-layer chromatography on silica gel (methylene chloride). At the completion of the reaction, add 400 ml of saturated aqueous sodium chloride, separate layers, and extract aqueous layer with ether (2×100 ml). Wash the combined ether solutions with water, dry over magnesium sulfate and evaporate. Triturate the oil residue with petroleum ether to provide the title compound. after completion of addition the progress of the reaction by thin-layer chromatography on silica gel (methylene chloride) At the completion of the reaction separate layers extract aqueous layer with ether (2×100 ml) Wash the combined ether solutions with water dry over magnesium sulfate evaporate Triturate the oil residue with petroleum ether

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

Procedure: Place 59 g (2.43 mole) of magnesium turnings into a four-neck flask equipped with mechanical stirrer under N2 atmosphere. Add 500 ml of anhydrous ether and then add a solution of 465 g (2.43 mole) of 1-bromo-4-chlorobenzene in 1000 ml of anhydrous ether dropwise while stirring. Stir one hour after the completion of addition. Transfer and add this Grignard reagent to a solution of 170 g (2.43 mole) of 1-methoxy-1,2-propanediene and 69 g of copper (I) bromide in 300 ml of anhydrous ether with cooling. Stir for another ten minutes after the completion of addition. Add saturated aqueous solution of ammonium hydroxide and decant ether solution. Wash the solid residue with ether (3×50 ml). Wash the combined ether solutions with 1N HCl, saturated aqueous sodium bicarbonate, and with H2O. Dry over magnesium sulfate, evaporate, and distill in vacuo to yield the title compound, b.p. 99°-105° C. (15 mmHg). Stir one hour after the completion of addition with cooling Stir for another ten minutes after the completion of addition Add saturated aqueous solution of ammonium hydroxide and decant ether solution Wash the solid residue with ether (3×50 ml) Wash the combined ether solutions with 1N HCl, saturated aqueous sodium bicarbonate Dry over magnesium sulfate evaporate distill in vacuo

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

Procedure: Under nitrogen and with cooling, to a solution of 150.6 g (1.0 mole) 1-chloro-4-(2-propynyl)benzene in 600 ml of anhydrous ether, add dropwise 400 ml of 2.5M n-butyllithium (1.0 mole) in hexane. When addition is complete, stir a further 30 minutes and under N2 add 31 g of para-formaldehyde. Stir the mixture in a dry ice/acetone bath for 1 hour. Allow to warm to room temperature and then allow to reflux. When the reaction is complete, add 400 ml of saturated aqueous sodium chloride. Separate the layers and extract the aqueous layer with ether. Wash the combined ether solution, wash with water and dry over magnesium sulfate. Evaporate off the ether, dissolve the residue in hot cyclohexane which yielded crystalline material the title compound. When addition Stir the mixture in a dry ice/acetone bath for 1 hour to reflux Separate the layers extract the aqueous layer with ether Wash the combined ether solution wash with water dry over magnesium sulfate Evaporate off the ether dissolve the residue in hot cyclohexane which

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

Procedure: In a flask containing 59 g (2.43 mole) magnesium turnings in 500 ml anhydrous ether under an atmosphere of nitroge add slowly a solution of 465 g (2.43 mole) of 4-bromochlorobenzene in 1 liter 4 anhydrous ether. With caution, once the Grignard has started maintain slow reflux until all 4-bromochlorobenzene has been added. Stir an additional hour and then add this Grignard (maintain slow reflux) to a suspension of 170 g (2.43 mole) methoxyallene and 69 g of cuprous bromide in 300 ml anhydrous ether under N2. When addition is complete, stir another 10 minutes and then add saturated ammonium chloride. Decant off the ether solution wash the solid residue with ether (3×50 ml). Combine the ether extracts and wash with 1N HCl, saturated aqueous sodium bicarbonate, water and dry over magnesium sulfate. Evaporate off the ether and distill the residue in vacuo to obtain the title compound (99-105mmHg). With caution, once the Grignard has started maintain slow has been added add this Grignard (maintain slow reflux) When addition stir another 10 minutes Decant off the ether solution wash the solid residue with ether (3×50 ml) Combine the ether extracts and wash with 1N HCl, saturated aqueous sodium bicarbonate, water dry over magnesium sulfate Evaporate off the ether distill the residue in vacuo

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

Procedure: Under nitrogen and with cooling, to a solution of 150.6 g (1.0 mole) 1-chloro-4-(2-propynyl)benzene in 600 ml of anhydrous ether, add dropwise 400 ml of 2.5M n-butyllithium (1.0 mole) in hexane. When addition is complete, stir a further 30 minutes and under N2 add 31 g of para-formaldehyde. Stir the mixture in a dry ice/acetone bath for 1 hour. Allow to warm to room temperature and then allow to reflux. When the reaction is complete, add 400 ml of saturated aqueous sodium chloride. Separate the layers and extract the aqueous layer with ether. Wash the combined ether solution, wash with water and dry over magnesium sulfate. Evaporate off the ether, dissolve the residue in hot cyclohexane which yielded crystalline material the title compound. When addition Stir the mixture in a dry ice/acetone bath for 1 hour to reflux Separate the layers extract the aqueous layer with ether Wash the combined ether solution wash with water dry over magnesium sulfate Evaporate off the ether dissolve the residue in hot cyclohexane which

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

Procedure: In a flask containing 59 g (2.43 mole) magnesium turnings in 500 ml anhydrous ether under an atmosphere of nitroge add slowly a solution of 465 g (2.43 mole) of 4-bromochlorobenzene in 1 liter 4 anhydrous ether. With caution, once the Grignard has started maintain slow reflux until all 4-bromochlorobenzene has been added. Stir an additional hour and then add this Grignard (maintain slow reflux) to a suspension of 170 g (2.43 mole) methoxyallene and 69 g of cuprous bromide in 300 ml anhydrous ether under N2. When addition is complete, stir another 10 minutes and then add saturated ammonium chloride. Decant off the ether solution wash the solid residue with ether (3×50 ml). Combine the ether extracts and wash with 1N HCl, saturated aqueous sodium bicarbonate, water and dry over magnesium sulfate. Evaporate off the ether and distill the residue in vacuo to obtain the title compound (99-105mmHg). With caution, once the Grignard has started maintain slow has been added add this Grignard (maintain slow reflux) When addition stir another 10 minutes Decant off the ether solution wash the solid residue with ether (3×50 ml) Combine the ether extracts and wash with 1N HCl, saturated aqueous sodium bicarbonate, water dry over magnesium sulfate Evaporate off the ether distill the residue in vacuo

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

Procedure: Under nitrogen and with cooling, to a solution of 150.6 g (1.0 mole) 1-chloro-4-(2-propynyl)benzene in 600 ml of anhydrous ether, add dropwise 400 ml of 2.5M n-butyllithium (1.0 mole) in hexane. When addition is complete, stir a further 30 minutes and under N2 add 31 g of para-formaldehyde. Stir the mixture in a dry ice/acetone bath for 1 hour. Allow to warm to room temperature and then allow to reflux. When the reaction is complete, add 400 ml of saturated aqueous sodium chloride. Separate the layers and extract the aqueous layer with ether. Wash the combined ether solution, wash with water and dry over magnesium sulfate. Evaporate off the ether, dissolve the residue in hot cyclohexane which yielded crystalline material the title compound. When addition Stir the mixture in a dry ice/acetone bath for 1 hour to reflux Separate the layers extract the aqueous layer with ether Wash the combined ether solution wash with water dry over magnesium sulfate Evaporate off the ether dissolve the residue in hot cyclohexane which

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

Procedure: In a flask containing 59 g (2.43 mole) magnesium turnings in 500 ml anhydrous ether under an atmosphere of nitroge add slowly a solution of 465 g (2.43 mole) of 4-bromochlorobenzene in 1 liter 4 anhydrous ether. With caution, once the Grignard has started maintain slow reflux until all 4-bromochlorobenzene has been added. Stir an additional hour and then add this Grignard (maintain slow reflux) to a suspension of 170 g (2.43 mole) methoxyallene and 69 g of cuprous bromide in 300 ml anhydrous ether under N2. When addition is complete, stir another 10 minutes and then add saturated ammonium chloride. Decant off the ether solution wash the solid residue with ether (3×50 ml). Combine the ether extracts and wash with lN HCl, saturated aqueous sodium bicarbonate, water and dry over magnesium sulfate. Evaporate off the ether and distill the residue in vacuo to obtain the title compound (99-105 mmHg). With caution, once the Grignard has started maintain slow has been added add this Grignard (maintain slow reflux) When addition stir another 10 minutes Decant off the ether solution wash the solid residue with ether (3×50 ml) Combine the ether extracts and wash with lN HCl, saturated aqueous sodium bicarbonate, water dry over magnesium sulfate Evaporate off the ether distill the residue in vacuo

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

Procedure: Under nitrogen and with cooling, to a solution of 150.6 g (1.0 mole) 1-chloro-4-(2-propynyl)benzene in 600 ml of anhydrous ether, add dropwise 400 ml of 2.5M n-butyllithium (1.0 mole) in hexane. When addition is complete, stir a further 30 minutes and under N2 add 31 g of para-formaldehyde. Stir the mixture in a dry ice/acetone bath for 1 hour. Allow to warm to room temperature and then allow to reflux. When the reaction is complete, add 400 ml of saturated aqueous sodium chloride. Separate the layers and extract the aqueous layer with ether. Wash the combined ether solution, wash with water and dry over magnesium sulfate. Evaporate off the ether, dissolve the residue in hot cyclohexane which yielded crystalline material the title compound. When addition Stir the mixture in a dry ice/acetone bath for 1 hour to reflux Separate the layers extract the aqueous layer with ether Wash the combined ether solution wash with water dry over magnesium sulfate Evaporate off the ether dissolve the residue in hot cyclohexane which

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

Procedure: In a flask containing 59 g (2.43 mole) magnesium turnings in 500 ml anhydrous ether under an atmosphere of nitrogen, and slowly a solution of 465 g (2.43 mole) of 4-bromochlorobenzene in 1 liter 4 anhydrous ether. With caution, once the Grignard has started maintain slow reflux until all 4-bromochlorobenzene has been added. Stir an additional hour and then add this Grignard (maintain slow reflux) to a suspension of 170 g (2.43 mole) methoxyallene and 69 g of cuprous bromide in 300 ml anhydrous ether under N2. When addition is complete, stir another 10 minutes and then add saturated ammonium chloride. Decant off the ether solution wash the solid residue with ether (3×50 ml). Combine the ether extracts and wash with 1N HCl, saturated aqueous sodium bicarbonate, water and dry over magnesium sulfate. Evaporate off the ether and distill the residue in vacuo to obtain the title compound (99-105 mmHg). With caution, once the Grignard has started maintain slow has been added add this Grignard (maintain slow reflux) When addition stir another 10 minutes Decant off the ether solution wash the solid residue with ether (3×50 ml) Combine the ether extracts and wash with 1N HCl, saturated aqueous sodium bicarbonate, water dry over magnesium sulfate Evaporate off the ether distill the residue in vacuo

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

Procedure: Dissolve 150.6 g (1.00 mole) of 1-chloro-4-(2-propynyl)benzene in 600 ml of anhydrous ether under N2 atmosphere with stirring at dry ice/acetone temperature. Add dropwise a solution of 400 ml of n-butyllithium (2.5M in hexane) (1.00 mole). Stir for an additional 30 minutes after completion of addition. Add 31 g (1.00 mole) of paraformaldehyde. Stir the mixture at dry ice/acetone temperature for 1 hour, and allow to warm to room temperature. Follow the progress of the reaction by thin-layer chromatography on silica gel (methylene chloride). At the completion of the reaction, add 400 ml of saturated aqueous sodium chloride, separate layers, and extract aqueous layer with ether (2×100 ml). Wash the combined ether solutions with water, dry over magnesium sulfate and evaporate. Triturate the oil residue with petroleum ether to provide the title compound. after completion of addition the progress of the reaction by thin-layer chromatography on silica gel (methylene chloride) At the completion of the reaction separate layers extract aqueous layer with ether (2×100 ml) Wash the combined ether solutions with water dry over magnesium sulfate evaporate Triturate the oil residue with petroleum ether