potassium;butan-1-olate

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 9.00 g (72.2 mmol) of 50% potassium butoxide, 200 ml of anhydrous tetrahydrofuran was added in the atmosphere of argon. To the mixture, cooled to 0° C., was added dropwise a solution of 25.81 g (72.2 mmol) of triethyl-4-phosphocrotonate dissolved in 30 ml of anhydrous tetrahydrofuran through a dropping funnel over 30 minutes. After 30 min., a solution of 10 g (60.2 mmol) of 2,4-dimethoxybenzaldehyde dissolved in 30 ml of anhydrous tetrahydrofuran was added dropwise through a dropping funnel over 10 minutes. Temperature of the reaction mixture was raised from 0° C. to room temperature followed by stirring for 18 hours. To the resulting mixture were successively added saturated aqueous solution of ammonium chloride and water followed by extraction with ethyl acetate. The organic layer was washed with water and saturated aqueous solution of ammonium chloride, then dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a residue. It was subjected to column chromatography on silica, and from the ethyl acetate-hexane (1:7) eluate fraction was produced 9.44 g (36.0 mmol) of ethyl 5-(2,4-dimethoxyphenyl)-2,4-pentadienoate. was added dropwise through a dropping funnel over 10 minutes Temperature of the reaction mixture was raised from 0° C. to room temperature followed by extraction with ethyl acetate The organic layer was washed with water and saturated aqueous solution of ammonium chloride dried over anhydrous magnesium sulfate concentrated under reduced pressure to obtain a residue

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixed solution of 15 ml of a THF solution and 1.5 ml of tert-butanol containing 309 mg of potassium-butoxide was added slowly in a nitrogen stream at 0° C. 300 mg of the compound prepared in (7) above dissolved in 7.5 ml of THF. After stirring for 10 minutes at the same temperature, 0.22 ml of n-butyl nitrite was dropwise added to the mixture, followed by further stirring for 1.5 hours, during which the temperature was slowly raised to 20° C. The reaction mixture was adjusted to pH 1 with the addition of 1N hydrochloric acid, extracted with chloroform, washed with saturated brine, and dried over anhydrous sodium sulfate. To the residue obtained by evaporating the solvent-was added a mixture of 15 ml of acetic acid and 15 ml of acetic anhydride, and was added about 1 gm of zinc powder, followed by stirring at 20° C. for 18 hours. Insoluble substances were removed by filtration, the solvent was evaporated, and the residue was extracted with chloroform. The extract was washed with saturated brine and dried over anhydrous sodium sulfate. After evaporating the solvent, the residue was subjected to silica gel column chromatography using a chloroform-methanol (97:3) mixed solvent as an eluant to obtain fractions containing the target compound. The fractions were concentrated to produce 311 mg of the title compound. was dropwise added to the mixture extracted with chloroform washed with saturated brine dried over anhydrous sodium sulfate To the residue obtained by evaporating the solvent-was added a mixture of 15 ml of acetic acid and 15 ml of acetic anhydride was added about 1 gm of zinc powder by stirring at 20° C. for 18 hours Insoluble substances were removed by filtration the solvent was evaporated the residue was extracted with chloroform The extract was washed with saturated brine dried over anhydrous sodium sulfate After evaporating the solvent mixed solvent as an eluant to obtain fractions containing the target compound The fractions were concentrated

Conditions: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-(Cyclopropylcarbonyl)phenylacetonitrile, 15.5 g [JOC, 1973,16, 487] and methyl iodide, 15.5 ml, are dissolved in 75 ml THF. The mixture is cooled to −10° C. and a solution of potassium butoxide (24.5 g) in THF (75 ml) is added so that the temperature of the reaction is kept below 5° C. After 0.5 h more, HPLC shows the reaction to be complete. 200 ml 2M HCI is added followed by 200 ml toluene. The organics are washed with 100 ml 10%. sodium sulphite solution then 100 ml satd sodium chloride solution. The THF is removed and the toluene treated with 5 g silica to remove colour. The toluene is removed and the product crystallises. Yield, 19 g. is kept below 5° C the reaction 200 ml 2M HCI is added The organics are washed with 100 ml 10% The THF is removed the toluene treated with 5 g silica to remove colour The toluene is removed the product crystallises Yield

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

Procedure: testosterone (XII) is reacted with potassium butoxide and methyl iodide to form 4-methyl-17β-hydroxyandrost-4-en-3-one

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

Procedure: testosterone (XII) is reacted with potassium butoxide and methyl iodide to form 4-methyl-17β-hydroxyandrost-4-en-3-one

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

Procedure: Butanediol (40 ml; 40.68 g; 0.452 mol) was stirred in a 100 ml round bottomed flask, and treated portionwise with potassium butoxide (17.60 g; 0.144 mol). The initial reaction was exothermic. The reaction mixture was stirred for 1.5 hours at room temperature. The resulting cloudy solution was then treated with chloromethyl styrene (20.00 g; 0.131 mol). The styrene formed an upper, pale green layer, (the colouration being due to the presence of inhibitor), whose color darkened considerably on the addition of 18-crown-6 (0.49 g; 1.86×10-3 mole). The flask was stoppered, protected from light, and stirred for 28 hours at room temperature. The mixture was then poured into water (120 ml) and extracted with dichloromethane (4×50 ml). The combined organic extracts were dried (MgSO4) and evaporated to give viscous yellow oil (932.7 g). This oil was distilled from a small amount of CuCl to give a product showing some impurities on TLC. The oil was then chromatographed on silica gel, initially eluting with dichloromethane/petrol (1:1) to remove the impurities. The product was then eluted off the column with ethyl acetate/petrol (1:1). Evaporation of the solvent gave a colourless oil, which was distilled to give the desired styrylbutyl alcohol as a colourless oil b.pt. 150°-152°/0.4 mbar. Yield 18.70 g; 69.2%. The initial reaction

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

Procedure: Butanediol (40 ml; 40.68 g; 0.452 mol) was stirred in a 100 ml round bottomed flask, and treated portionwise with potassium butoxide (17.60 g; 0.144 mol). The initial reaction was exothermic. The reaction mixture was stirred for 1.5 hours at room temperature. The resulting cloudy solution was then treated with chloromethyl styrene (20.00 g; 0.131 mol). The styrene formed an upper, pale green layer, (the colouration being due to the presence of inhibitor), whose color darkened considerably on the addition of 18-crown-6 (0.49 g; 1.86×10-3 mole). The flask was stoppered, protected from light, and stirred for 28 hours at room temperature. The mixture was then poured into water (120 ml) and extracted with dichloromethane (4×50 ml). The combined organic extracts were dried (MgSO4) and evaporated to give viscous yellow oil (932.7 g). This oil was distilled from a small amount of CuCl to give a product showing some impurities on TLC. The oil was then chromatographed on silica gel, initially eluting with dichloromethane/petrol (1:1) to remove the impurities. The product was then eluted off the column with ethyl acetate/petrol (1:1). Evaporation of the solvent gave a colourless oil, which was distilled to give the desired styrylbutyl alcohol as a colourless oil b.pt. 150°-152°/0.4 mbar. Yield 18.70 g; 69.2%. The initial reaction

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

Procedure: Potassium butoxide (0.5 g) was added to a THF (10 mL) solution of allyl 2-{3-(2,6-difluorophenyl)pyrazol-1-yl}acetate (0.5 g) and 5-chloro-1-methyl-3-trifluoromethylpyrazole-4-carbonyl chloride (0.44 g) at 0° C. and stirred for 5 minutes. Water (5 ml) was added thereto, and then extracted with diluted hydrochloric acid and ethyl acetate. After the organic layer was dried over anhydrous magnesium sulfate, and then concentrated, and the resulting concentrate was purified through silica gel column chromatography (chloroform) to obtain the intended product, Compound No. I-133 (0.89 g). extracted with diluted hydrochloric acid and ethyl acetate After the organic layer was dried over anhydrous magnesium sulfate concentrated the resulting concentrate was purified through silica gel column chromatography (chloroform) to obtain the intended product, Compound No

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

Procedure: Potassium butoxide (0.5 g) was added to a THF (10 mL) solution of allyl 2-{3-(2,6-difluorophenyl)pyrazol-1-yl}acetate (0.5 g) and 5-chloro-1-methyl-3-trifluoromethylpyrazole-4-carbonyl chloride (0.44 g) at 0° C. and stirred for 5 minutes. Water (5 ml) was added thereto, and then extracted with diluted hydrochloric acid and ethyl acetate. After the organic layer was dried over anhydrous magnesium sulfate, and then concentrated, and the resulting concentrate was purified through silica gel column chromatography (chloroform) to obtain the intended product, Compound No. I-133 (0.89 g). extracted with diluted hydrochloric acid and ethyl acetate After the organic layer was dried over anhydrous magnesium sulfate concentrated the resulting concentrate was purified through silica gel column chromatography (chloroform) to obtain the intended product, Compound No

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixed solution of 15 ml of a THF solution and 1.5 ml of tert-butanol containing 309 mg of potassium-butoxide was added slowly in a nitrogen stream at 0° C. 300 mg of the compound prepared in (7) above dissolved in 7.5 ml of THF. After stirring for 10 minutes at the same temperature, 0.22 ml of n-butyl nitrite was dropwise added to the mixture, followed by further stirring for 1.5 hours, during which the temperature was slowly raised to 20° C. The reaction mixture was adjusted to pH 1 with the addition of 1N hydrochloric acid, extracted with chloroform, washed with saturated brine, and dried over anhydrous sodium sulfate. To the residue obtained by evaporating the solvent was added a mixture of 15 ml of acetic acid and 15 ml of acetic anhydride, and was added about 1 gm of zinc powder, followed by stirring at 20° C. for 18 hours. Insoluble substances were removed by filtration, the solvent was evaporated, and the residue was extracted with chloroform. The extract was washed with saturated brine and dried over anhydrous sodium sulfate. After evaporating the solvent, the residue was subjected to silica gel column chromatography using a chloroform-methanol (97:3) mixed solvent as an eluant to obtain fractions containing the target compound. The fractions were concentrated to produce 311 mg of the title compound. was dropwise added to the mixture extracted with chloroform washed with saturated brine dried over anhydrous sodium sulfate To the residue obtained by evaporating the solvent was added a mixture of 15 ml of acetic acid and 15 ml of acetic anhydride was added about 1 gm of zinc powder by stirring at 20° C. for 18 hours Insoluble substances were removed by filtration the solvent was evaporated the residue was extracted with chloroform The extract was washed with saturated brine dried over anhydrous sodium sulfate After evaporating the solvent mixed solvent as an eluant to obtain fractions containing the target compound The fractions were concentrated

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

Procedure: 4-nitro-fluorobenzene and 2-(carboxymethoxy)phenol were reacted together in DMA in the presence of potassium butoxide for 2 hours at 150° C. to yield 4-(2-carboxymethoxy-phenoxy)nitrobenzene, intermediate 1.

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

Procedure: 4-nitro-fluorobenzene and 2-(carboxymethoxy)phenol were reacted together in DMA in the presence of potassium butoxide for 2 hours at 150° C. to yield 4-(2-carboxymethoxy)-phenoxy)nitrobenzene.