2-cyclopentyl-1-(2,3-dichloro-4-methoxyphenyl)ethanone

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

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

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

Procedure: 2',3'-Dichloro-4'-methoxy-2-cyclopentylacetophenone (51.6 g., 0.18 mole) is dissolved in dioxane (460 ml.) and paraformaldehyde (21.6 g., 0.72 mole) and concentrated sulfuric acid (9.65 g.) are added. The mixture is heated at 80°-85° C. for 20 hours. The dioxane is evaporated at reduced pressure. Water is added to the residual gum which then is extracted into ether. The ether extract is washed with water and dried over magnesium sulfate. The ether is evaporated and upon triturating the residue with hexane (5 ml.) there is obtained a solid that is crystallized from ligroin to obtain 2',3'-dichloro-4'-methoxy-2-cyclopentylacrylophenone (33.3 g.), m.p. 59°-63° C. Crystallization from butyl chloride affords a sample (m.p. 66°-67.5° C.) for analysis. The mixture is heated at 80°-85° C. for 20 hours The dioxane is evaporated at reduced pressure Water is added to the residual gum which then is extracted into ether The ether extract is washed with water dried over magnesium sulfate The ether is evaporated upon triturating the residue with hexane (5 ml.) there is obtained a solid that is crystallized from ligroin

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

Procedure: 2,3-Dichloroanisole (57.8 g., 0.327 mole) is dissolved in dichloromethane (300 ml.) and cyclopentylacetyl chloride (52.7 g., 0.367 mole) is added. The solution is cooled to +5° C. and aluminum chloride (48.0 g., 0.36 mole) is added gradually over a one-hour period at +5° C. The mixture is stirred for 2 hours at +5° C. and at 20°-25° C. for 16 hours and then poured into 1 liter of ice water containing 150 ml. of 12N hydrochloric acid. The organic phase is separated and the aqueous phase is extracted with dichloromethane. The combined organic phases are washed with sodium chloride solution, 10% sodium hydroxide and again with sodium chloride solution and dried over magnesium sulfate. On evaporation of the solvent a brown solid is obtained which is crystallized from hexane to obtain 53.2 of 2',3'-dichloro-4'-methoxy-2-cyclopentylacetophenone, m.p. 60°-61.5° C. The solution is cooled to +5° C. The organic phase is separated the aqueous phase is extracted with dichloromethane The combined organic phases are washed with sodium chloride solution, 10% sodium hydroxide and again with sodium chloride solution dried over magnesium sulfate On evaporation of the solvent a brown solid is obtained which is crystallized from hexane

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

Procedure: 2,3-Dichloroanisole (57.8 g., 0.327 mole) is dissolved in dichloromethane (300 ml.) and cyclopentylacetyl chloride (52.7 g., 0.367 mole) is added. The solution is cooled to +5° C. and aluminum chloride (48.0 g., 0.36 mole) is added gradually over a one-hour period at +5° C. The mixture is stirred for 2 hours at +5° C. and at 20°-25° C. for 16 hours and then poured into 1 liter of ice water containing 150 ml. of 12N hydrochloric acid. The organic phase is separated and the aqueous phase is extracted with dichloromethane. The combined organic phases are washed with sodium chloride solution, 10% sodium hydroxide and again with sodium chloride solution and dried over magnesium sulfate. On evaporation of the solvent a brown solid is obtained which is crystallized from hexane to obtain 53.2 of 2',3'-dichloro-4'-methoxy-2-cyclopentylacetophenone, m.p. 60°-61.5° C. The solution is cooled to +5° C. The organic phase is separated the aqueous phase is extracted with dichloromethane The combined organic phases are washed with sodium chloride solution, 10% sodium hydroxide and again with sodium chloride solution dried over magnesium sulfate On evaporation of the solvent a brown solid is obtained which is crystallized from hexane

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

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

Procedure: 2',3'-Dichloro-4'-methoxy-2-cyclopentyl-acetophenone (51.6 g., 0.18 mole) is dissolved in dioxane (460 ml.) and paraformaldehyde (21.6 g., 0.72 mole) and concentrated sulfuric acid (9.65 g.) are added. The mixture is heated at 80°-85°C. for 20 hours. The dioxane is evaporated at reduced pressure. Water is added to the residual gum which then is extracted into ether. The ether extract is washed with water and dried over magnesium sulfate. The ether is evaporated and upon triturating the residue with hexane (5 ml.) there is obtained a solid that is crystallized from ligroin to obtain (33.3 g.), m.p. 59°-63°C. Crystallization from butyl chloride affords a sample (m.p. 66°-67.5°C.) for analysis. The mixture is heated at 80°-85°C. for 20 hours The dioxane is evaporated at reduced pressure Water is added to the residual gum which then is extracted into ether The ether extract is washed with water dried over magnesium sulfate The ether is evaporated upon triturating the residue with hexane (5 ml.) there is obtained a solid that is crystallized from ligroin to obtain (33.3 g.), m.p. 59°-63°C Crystallization from butyl chloride affords a sample (m.p. 66°-67.5°C.) for analysis

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

Procedure: 2',3'-Dichloro-4'-methoxy-2-cyclopentylacetophenone (51.6 g., 0.18 mole) is dissolved in dioxane (460 ml.) and paraformaldehyde (21.6 g., 0.72 mole) and concentrated sulfuric acid (9.65 g.) are added. The mixture is heated at 80°-85° C. for 20 hours. The dioxane is evaporated at reduced pressure. Water is added to the residual gum which then is extracted into ether. The ether extract is washed with water and dried over magnesium sulfate. The ether is evaporated and upon triturating the residue with hexane (5 ml.) there is obtained a solid that is crystallized from ligroin to obtain 2',3'-dichloro-4'-methoxy-2-cyclopentylacrylophenone (33.3 g.), m.p. 59°-63° C. Crystallization from butyl chloride affords a sample (m.p. 66°-67.5° C.) for analysis. The mixture is heated at 80°-85° C. for 20 hours The dioxane is evaporated at reduced pressure Water is added to the residual gum which then is extracted into ether The ether extract is washed with water dried over magnesium sulfate The ether is evaporated upon triturating the residue with hexane (5 ml.) there is obtained a solid that is crystallized from ligroin

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

Procedure: 2,3-Dichloroanisole (57.8 g., 0.327 mole) is dissolved in dichloromethane (300 ml.) and cyclopentylacetyl chloride (52.7 g., 0.367 mole) is added. The solution is cooled to +5° C. and aluminum chloride (48.0 g., 0.36 mole) is added gradually over a one-hour period at +5° C. The mixture is stirred for 2 hours at +5° C. and at 20°-25° C. for 16 hours and then poured into 1 liter of ice water containing 150 ml. of 12N hydrochloric acid. The organic phase is separated and the aqueous phase is extracted with dichloromethane. The combined organic phases are washed with sodium chloride solution, 10% sodium hydroxide and again with sodium chloride solution and dried over magnesium sulfate. On evaporation of the solvent a brown solid is obtained which is crystallized from hexane to obtain 53.2 of 2',3'-dichloro-4'-methoxy-2-cyclopentylacetophenone, m.p. 60°-61.5° C. The solution is cooled to +5° C. The organic phase is separated the aqueous phase is extracted with dichloromethane The combined organic phases are washed with sodium chloride solution, 10% sodium hydroxide and again with sodium chloride solution dried over magnesium sulfate On evaporation of the solvent a brown solid is obtained which is crystallized from hexane