O-[(E)-3-chloroprop-2-enyl]hydroxylamine

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

Procedure: In this example, 29.5 g (0.1151 mol) of 2-acetyl-5-(2-ethylthiopropyl)cyclohexane-1,3-dione; 1.7 g (0.0277 mol) of acetic acid, and 19.7 g (0.1369 mol) of 3-trans-chloroallyloxyamine in 62 ml of water were admixed to 37 ml of hexane. Aqueous 5 wt. % sodium hydroxide was slowly added dropwise over about 15 minutes until 5.5 g (0.1369 m+small excess) of sodium hydroxide had been added yielding a reaction mixture pH of about 6. The mixture was heated to and maintained at 40° C. for 21/2 hours and then cooled to room temperature. The organic (i.e., hexane) phase was separated and washed with 16 ml of aqueous 5 wt. % hydrochloric acid and then aqueous 6.25 wt. % sodium hydroxide added until pH12. The aqueous phase was separated and admixed with 35 ml of hexane at about 0° C. (ice bath) and the pH adjusted to 5 by the dropwise addition of aqueous 36 wt. % hydrochloric acid over an ice bath. A few mls of methylene chloride was then added. The organic phase was separated, dried over magnesium sulfate and then concentrated by evaporation affording 35.2 g of a crude product as an oil. The crude product was purified by column chromatography over silica gel eluting with hexane:methylene chloride mixtures affording 17.4 g of the purified title compound also as an oil. Elemental analysis carbon calculated 55.56%, found 54.43%; Hydrogen calculated 6.99%, found 6.53%; Nitrogen 4.05%, found 4.31%. had been added

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

Procedure: In this example, 29.5 g (0.1151 mol) of 2-acetyl-5-(2-ethylthiopropyl)cyclohexane-1,3-dione; 1.7 g (0.0277 mol) of acetic acid, and 19.7 g (0.1369 mol) of 3-trans-chloroallyloxyamine in 62 ml of water were admixed to 37 ml of hexane. Aqueous 5 wt. % sodium hydroxide was slowly added dropwise over about 15 minutes until 5.5 g (0.1369 m+small excess) of sodium hydroxide had been added yielding a reaction mixture pH of about 6. The mixture was heated to and maintained at 40° C. for 21/2 hours and then cooled to room temperature. The organic (i.e., hexane) phase was separated and washed with 16 ml of aqueous 5 wt. % hydrochloric acid and then aqueous 6.25 wt. % sodium hydroxide added until pH12. The aqueous phase was separated and admixed with 35 ml of hexane at about 0° C. (ice bath) and the pH adjusted to 5 by the dropwise addition of aqueous 36 wt. % hydrochloric acid over an ice bath. A few mls of methylene chloride was then added. The organic phase was separated, dried over magnesium sulfate and then concentrated by evaporation affording 35.2 g of a crude product as an oil. The crude product was purified by column chromatography over silica gel eluting with hexane:methylene chloride mixtures affording 17.4 g of the purified title compound also as an oil. Elemental analysis carbon calculated 55.56%, found 54.43%; Hydrogen calculated 6.99%, found 6.53%; Nitrogen 4.05%, found 4.31%. had been added

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

Procedure: In this example, 29.5 g (0.1151 mol) of 2-acetyl-5-(2-ethylthiopropyl)cyclohexane-1,3-dione; 1.7 g (0.0277 mol) of acetic acid, and 19.7 g (0.1369 mol) of 3-trans-chloroallyloxyamine in 62 ml of water were admixed to 37 ml of hexane. Aqueous 5 wt. % sodium hydroxide was slowly added dropwise over about 15 minutes until 5.5 g (0.1369 m+small excess) of sodium hydroxide had been added yielding a reaction mixture pH of about 6. The mixture was heated to and maintained at 40° C. for 21/2 hours and then cooled to room temperature. The organic (i.e., hexane) phase was separated and washed with 16 ml of aqueous 5 wt. % hydrochloric acid and then aqueous 6.25 wt. % sodium hydroxide added until pH12. The aqueous phase was separated and admixed with 35 ml of hexane at about 0° C. (ice bath) and the pH adjusted to 5 by the dropwise addition of aqueous 36 wt. % hydrochloric acid over an ice bath. A few mls of methylene chloride was then added. The organic phase was separated, dried over magnesium sulfate and then concentrated by evaporation affording 35.2 g of a crude product as an oil. The crude product was purified by column chromatography over silica gel eluting with hexane:methylene chloride mixtures affording 17.4 g of the purified title compound also as an oil. Elemental analysis carbon calculated 55.56%, found 54.43%; Hydrogen calculated 6.99%, found 6.53%; Nitrogen 4.05%, found 4.31%. had been added

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

Procedure: To 10 ml of a solution of 5.60 g (21.3 mmols) of 5-(1,3-dimethyl-1H-pyrazol-5-yl)-2-propionylcyclohexane-1,3-dione in methanol was added 57 ml (21.7 mmols) of 0.38 mol ethanolic solution of (E)-3-chloro-2-propenyloxyamine. The mixture was reacted for 10 hours with stirring. After completion of the reaction, the reaction mixture was concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (hexane:ethyl acetate=2:1) to give 6.84 g of the product. The mixture was reacted for 10 hours After completion of the reaction the reaction mixture was concentrated under reduced pressure The resulting crude product was purified by silica gel column chromatography (hexane:ethyl acetate=2:1)

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

Procedure: In 20 ml of ethanol was dissolved 2.62 g (10 mmols) of 5-(1,3-dimethyl-1H-pyrazol-4-yl)-2-propionylcyclohexane-1,3-dione and, 30 ml (12 mmols) of 0.4 mol ethanolic solution of (E)-3-chloro-2-propenyloxyamine was added to the solution. The mixture was reacted for 8 hours with stirring. After completion of the reaction, the reaction mixture was concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (chloroform:methanol=50:1) to give 3.21 g of the product. was added to the solution The mixture was reacted for 8 hours After completion of the reaction the reaction mixture was concentrated under reduced pressure The resulting crude product was purified by silica gel column chromatography (chloroform:methanol=50:1)

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

Procedure: To 5 ml of an ethanolic solution of 0.35 g (1.4 mmols) of 5-(1-methyl-1H-pyrazol-5-yl)-2-propionylcyclohexane-1,3-dione was added 3.8 ml (1.4 mmols) of 0.38 mol ethanolic solution of (E)-3-chloro-2-propenyloxyamine. The mixture was reacted for 10 hours with stirring. After completion of the reaction, the reaction mixture was concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (hexane:ethyl acetate=b 1:2) to give 0.25 g of the product. The mixture was reacted for 10 hours After completion of the reaction the reaction mixture was concentrated under reduced pressure The resulting crude product was purified by silica gel column chromatography (hexane:ethyl acetate=b 1:2)

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

Procedure: To 200 ml of an ethanolic solution of 20.0 g (81 mmols) of 5-(1-methyl-1H-pyrazol-4-yl)-2-propionylcyclohexane-1,3-dione was added 210 ml (84 mmols) of 0.4 mol ethanolic solution of (E)-3-chloro-2-propenyloxyamine. The mixture was reacted for 8 hours with stirring. After completion of the reaction, the reaction mixture was concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (ethyl acetate) to give 12.5 g of the product. The mixture was reacted for 8 hours After completion of the reaction the reaction mixture was concentrated under reduced pressure The resulting crude product was purified by silica gel column chromatography (ethyl acetate)

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

Procedure: In this example, 29.5 g (0.1151 mol) of 2-acetyl-5-(2-ethylthiopropyl)cyclohexane-1,3-dione; 1.7 g (0.0277 mol) of acetic acid, and 19.7 g (0.1369 mol) of 3-trans-chloroallyloxyamine in 62 ml of water were admixed to 37 ml of hexane. Aqueous 5 wt. % sodium hydroxide was slowly added dropwise over about 15 minutes until 5.5 g (0.1369 m+small excess) of sodium hydroxide had been added yielding a reaction mixture pH of about 6. The mixture was heated to and maintained at 40° C. for 21/2 hours and then cooled to room temperature. The organic (i.e., hexane) phase was separated and washed with 16 ml of aqueous 5 wt. % hydrochloric acid and then aqueous 6.25 wt. % sodium hydroxide added until pH12. The aqueous phase was separated and admixed with 35 ml of hexane at about 0° C. (ice bath) and the pH adjusted to 5 by the dropwise addition of aqueous 36 wt. % hydrochloric acid over an ice bath. A few mls of methylene chloride was then added. The organic phase was separated, dried over magnesium sulfate and then concentrated by evaporation affording 35.2 g of a crude product as an oil. The crude product was purified by column chromatography over silica gel eluting with hexane:methylene chloride mixtures affording 17.4 g of the purified title compound also as an oil. Elemental analysis carbon calculated 55.56%, found 54.43%; Hydrogen calculated 6.99%, found 6.53%; Nitrogen 4.05%, found 4.31%. had been added