N-[1-(4-chlorophenyl)ethylidene]hydroxylamine

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

Procedure: Hexafluoro-2-butyne is slowly bubbled through a 55°-60° C. solution of p-chloroacetophenone oxime (17.0 g, 0.10 mol), methanol (80 mL) and potassium tert-butoxide (1.12 g, 0.01 mol) over a 5 hour period. The solvent is removed in vacuo to obtain a liquid which is poured into water and extracted with ether. The combined organic extracts are washed sequentially with water and brine, dried over anhydrous sodium sulfate and concentrated in vacuo to give an oil. The oil is chromatographed using silica gel and eluted with 1% ethylacetate in methylene chloride to 5% ethyl acetate in methylene chloride to give p-chloro-0-[1,2-bis(trifluoromethyl)vinyl]acetophenone oxime, vinyl-(Z) as a yellow liquid (21.5 g, 65%) and 2-(p-chlorophenyl)-4,5-trans-bis(trifluoromethyl)-1-pyrrolin-5-ol as a white solid (2.35 g, mp 152.5°-153° C., 7%). The solvent is removed in vacuo to obtain a liquid which extracted with ether The combined organic extracts are washed sequentially with water and brine dried over anhydrous sodium sulfate concentrated in vacuo to give an oil The oil is chromatographed eluted with 1% ethylacetate in methylene chloride to 5% ethyl acetate in methylene chloride

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

Procedure: Hexafluoro-2-butyne is slowly bubbled through a 55°-60° C. solution of p-chloroacetophenone oxime (17.0 g, 0.10 mol), methanol (80 mL) and potassium tert-butoxide (1.12 g, 0.01 mol) over a 5 hour period. The solvent is removed in vacuo to obtain a liquid which is poured into water and extracted with ether. The combined organic extracts are washed sequentially with water and brine, dried over anhydrous sodium sulfate and concentrated in vacuo to give an oil. The oil is chromatographed using silica gel and eluted with ethylacetate in methylene chloride to 5% ethyl acetate in methylene chloride to give p-chloro-0-[1,2-bis(trifluoromethyl)vinyl]acetophenone oxime, vinyl-(Z) as a yellow liquid (21.5 g, 65%) and 2-(p-chlorophenyl)-4,5-trans-bis(trifluoromethyl)-1-pyrrolin-5-ol as a white solid (2.35 g, mp 152.5°-153° C., 7%). The solvent is removed in vacuo to obtain a liquid which extracted with ether The combined organic extracts are washed sequentially with water and brine dried over anhydrous sodium sulfate concentrated in vacuo to give an oil The oil is chromatographed eluted with ethylacetate in methylene chloride to 5% ethyl acetate in methylene chloride

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

Procedure: A solution of 2.4 g of sodium hydroxide in 55 ml of 85% ethanol was mixed with 6,78 g of 4'-chloroacetophenone oxime and 2.88 g of acrylic acid. The mixture was then refluxed for 2.5 hours, subsequently diluted with 10 ml of water, and concentrated by evaporation in a vacuum after 2 hours. The residue was dissolved in 50 ml of ether and 50 ml of water, and the layers were separated. The water layer was extracted with 50 ml of ether and then acidified with 40 ml of 2 N hydrochloric acid. The acid solution was extracted with 100 ml of ether and the ethereal solution was dried over sodium sulfate. Then the solvent was distilled off and its last traces were removed together with higher boiling substances at a pressure of 0.01 mm and a temperature of 50° C. The residue was crystallized from petroleum ether. Melting point 80° C.-83° C. The mixture was then refluxed for 2.5 hours concentrated by evaporation in a vacuum after 2 hours The residue was dissolved in 50 ml of ether 50 ml of water, and the layers were separated The water layer was extracted with 50 ml of ether The acid solution was extracted with 100 ml of ether the ethereal solution was dried over sodium sulfate Then the solvent was distilled off its last traces were removed together with higher boiling substances at a pressure of 0.01 mm a temperature of 50° C The residue was crystallized from petroleum ether

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

Procedure: Of the (α-methyl-4-chlorobenzylidene amino)oxy acetonitrile (melting point 57° C.-58.5° C.) which was obtained by reacting the sodium salt of 4'-chloroacetophenone oxime, with chloroacetonitrile in dimethylformamide, an amount of 11.3 g was dissolved in diisopropyl ether in which 1.94 g of hydrogen chloride and 1.73 g of methanol had also been dissolved. The solution was diluted with 25 ml of diisopropyl ether and subsequently stirred over night. Then the precipitate was drawn off, washed with absolute ether and dried in a vacuum. The resulting hydrochloride of methyl (α-methyl-4-chlorobenzylidene amino)oxy acetimidate melted at 95° C. with decomposition. After this substance had been dissolved in water, the superscribed ester separated out from the solution. It was extracted with ether and distilled in a vacuum. Boiling point at a pressure of 0.1 mm: 130° C.-132° C. had also been dissolved washed with absolute ether dried in a vacuum After this substance had been dissolved in water the superscribed ester separated out from the solution It was extracted with ether distilled in a vacuum 130° C.-132° C.

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

Procedure: Hexafluoro-2-butyne is slowly bubbled through a 55°-60° C. solution of p-chloroacetophenone oxime (17.0 g, 0.10 mol), methanol (80 mL) and potassium tert-butoxide (1.12 g, 0.01 mol) over a 5 hour period. The solvent is removed in vacuo to obtain a liquid which is poured into water and extracted with ether. The combined organic extracts are washed sequentially with water and brine, dried over anhydrous sodium sulfate and concentrated in vacuo to give an oil. The oil is chromatographed using silica gel and eluted with 1% ethylacetate in methylene chloride to 5% ethyl acetate in methylene chloride to give p-chloro-0-[1,2-bis(trifluoromethyl)vinyl]acetophenone oxime, vinyl-(Z) as a yellow liquid (21.5 g, 65%) and 2-(p-chlorophenyl)-4,5-trans-bis(trifluoromethyl)-1-pyrrolin-5-ol as a white solid (2.35 g, mp 152.5°-153° C., 7%). The solvent is removed in vacuo to obtain a liquid which extracted with ether The combined organic extracts are washed sequentially with water and brine dried over anhydrous sodium sulfate concentrated in vacuo to give an oil The oil is chromatographed eluted with 1% ethylacetate in methylene chloride to 5% ethyl acetate in methylene chloride

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

Procedure: Hexafluoro-2-butyne is slowly bubbled through a 55°-60° C. solution of p-chloroacetophenone oxime (17.0 g, 0.10 mol), methanol (80 mL) and potassium tert-butoxide (1.12 g, 0.01 mol) over a 5 hour period. The solvent is removed in vacuo to obtain a liquid which is poured into water and extracted with ether. The combined organic extracts are washed sequentially with water and brine, dried over anhydrous sodium sulfate and concentrated in vacuo to give an oil. The oil is chromatographed using silica gel and eluted with 1% ethylacetate in methylene chloride to 5% ethyl acetate in methylene chloride to give p-chloro-0-[1,2-bis(trifluoromethyl)vinyl]acetophenone oxime, vinyl-(Z) as a yellow liquid (21.5 g, 65%) and 2-(p-chlorophenyl)-4,5-trans-bis(trifluoromethyl)-1-pyrrolin-5-ol as a white solid (2.35 g, mp 152.5°-153° C., 7%). The solvent is removed in vacuo to obtain a liquid which extracted with ether The combined organic extracts are washed sequentially with water and brine dried over anhydrous sodium sulfate concentrated in vacuo to give an oil The oil is chromatographed eluted with 1% ethylacetate in methylene chloride to 5% ethyl acetate in methylene chloride

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

Procedure: Hexafluoro-2-butyne is slowly bubbled through a 55°-60° C. solution of p-chloroacetophenone oxime (17.0 g, 0.10 mol), methanol (80 mL) and potassium tert-butoxide (1.12 g, 0.01 mol) over a 5 hour period. The solvent is removed in vacuo to obtain a liquid which is poured into water and extracted with ether. The combined organic extracts are washed sequentially with water and brine, dried over anhydrous sodium sulfate and concentrated in vacuo to give an oil. The oil is chromatographed using silica gel and eluted with ethylacetate in methylene chloride to 5% ethyl acetate in methylene chloride to give p-chloro-0-[1,2-bis(trifluoromethyl)vinyl]acetophenone oxime, vinyl-(Z) as a yellow liquid (21.5 g, 65%) and 2-(p-chlorophenyl)-4,5-trans-bis(trifluoromethyl)-1-pyrrolin-5-ol as a white solid (2.35 g, mp 152.5°-153° C., 7%). The solvent is removed in vacuo to obtain a liquid which extracted with ether The combined organic extracts are washed sequentially with water and brine dried over anhydrous sodium sulfate concentrated in vacuo to give an oil The oil is chromatographed eluted with ethylacetate in methylene chloride to 5% ethyl acetate in methylene chloride