O-ethylhydroxylamine;hydrochloride

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 0.4 Gram of 2-acetyl-5-[1-methyl-2-(4-trifluoromethylphenylthio)ethyl]cyclohexane-1,3-dione and 0.1 g of ethoxyamine hydrochloride were dissolved in 10 ml of methanol and 0.15 g of potassium carbonate was added to the resulting solution which was then refluxed for 3 hours. The reaction solution was poured into water and extracted with chloroform. After removing chloroform, the residue was purified by thin layer chromatography (eluent, hexane:ethyl acetate=5:1) to obtain 0.3 g of 2-(1-ethoxyaminoethylidene)-5-[1-methyl-2-(4-trifluoromethylphenylthio)ethyl]cyclohexane-1,3-dione. was then refluxed for 3 hours extracted with chloroform After removing chloroform the residue was purified by thin layer chromatography (eluent, hexane:ethyl acetate=5:1)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 0.27 Gram of 2-propionyl-5-[2-(4-trifluoromethylphenylthio)propyl]cyclohexane-1,3-dione was dissolved in 10 ml of ethyl acetate, and 0.08 g of ethoxyamine hydrochloride and 0.1 g of N,N-diethylaniline were added to the resulting solution which was then refluxed for 5 hours. The reaction solution was cooled to room temperature, poured into water, weakly acidified and extracted with ethyl acetate. The ethyl acetate layer was washed with dilute hydrochloric acid and water subsequently and dried over anhydrous magnsium sulfate. After removing ethyl acetate, the residue was purified by thin layer chromatography (eluent, hexane:ethyl acetate=5:1) to obtain 0.13 g of 2-(1-ethoxyaminopropylidene)-5-[2-(4-trifluoromethylphenylthio)propyl]cyclohexane-1,3-dione. was then refluxed for 5 hours extracted with ethyl acetate The ethyl acetate layer was washed with dilute hydrochloric acid and water subsequently dried over anhydrous magnsium sulfate After removing ethyl acetate the residue was purified by thin layer chromatography (eluent, hexane:ethyl acetate=5:1)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 0.21 Gram of 2-propionyl-5-[2-(4-α,α,β,β-tetrafluoroethoxyphenylthio)ethyl]cyclohexane-1,3-dione was dissolved in 10 ml of ethanol, and 0.06 g of ethoxyamine hydrochloride and 0.06 g of triethylamine were added to the resulting solution which was then stirred overnight at room temperature. The reaction solution was poured into water, acidified with dilute hydrochloric acid and extracted with chloroform. Chloroform was removed and the residue was purified by thin layer chromatography (developing solvent, hexane:ethyl acetate=5:1) to obtain 0.07 g of 2-(1-ethoxyaminopropylidene)-5-[2-(4-α,α,β,β-tetrafluoroethoxyphenylthio)ethyl]cyclohexane-1,3-dione. extracted with chloroform Chloroform was removed the residue was purified by thin layer chromatography (developing solvent, hexane:ethyl acetate=5:1)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 0.19 Gram of 2-acetyl-5-[2-(4-trifluoromethoxyphenylthio)ethyl]cyclohexane-1,3-dione was dissolved in 10 ml of ethanol, and 0.07 g of ethoxyamine hydrochloride and 0.06 g of triethylamine were added to the resulting solution which was then stirred overnight at room temperature. The reaction solution was poured into water, acidified with dilute hydrochloric acid and extracted with chloroform. Chloroform was removed and the residue was purified by thin layer chromatography (eluent, hexane:ethyl acetate=5:1) to obtain 0.12 g of 2-(1-ethoxyaminoethylidene)-5-[2-(4-trifluoromethoxyphenylthio)ethyl]cyclohexane-1,3-dione. extracted with chloroform Chloroform was removed the residue was purified by thin layer chromatography (eluent, hexane:ethyl acetate=5:1)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2.1 Grams of 2-acetyl-5-[2-(4-trifluoromethylphenylthio)ethyl]cyclohexane-1,3-dione was dissolved in 10 ml of ethanol, and 0.71 g of ethoxyamine hydrochloride and 0.68 g of triethylamine were added to the resulting solution which was then stirred overnight at room temperature. The reaction solution was poured into water, acidified with dilute hydrochloric acid and extracted with chloroform. Chloroform was removed and the residue was purified by column chromatography on silica gel (eluent, ethyl acetate:hexane=1:5) to obtain 1.2 g of 2-(1-ethoxyaminoethylidene)-5-[2-(4-trifluoromethylphenylthio)ethyl]cyclohexane-1,3-dione as white crystals. extracted with chloroform Chloroform was removed the residue was purified by column chromatography on silica gel (eluent, ethyl acetate:hexane=1:5)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 0.6 Gram of 2-butyryl-5-[2-(5-trifluoromethyl-2-pyridylthio)ethyl]cyclohexane-1,3-dione was dissolved in a mixed solvent of 10 ml of ethanol and 1 ml of water, and 0.2 g of ethoxyamine hydrochloride and 0.07 g of sodium hydroxide were added to the resulting solution which was then stirred at room temperature for 2.5 hours. The reaction solution was poured into water, weakly acidified and extracted with ethyl acetate. After removing ethyl acetate, the residue was purified by thin layer chromatography (eluent, hexane:ethyl acetate=5:1) to obtain 0.45 g of 2-(1-ethoxyaminobutylidene)-5-[2-(5-trifluoromethyl-2-pyridylthio)ethyl]cyclohexane-1,3-dione. were added to the resulting solution which extracted with ethyl acetate After removing ethyl acetate the residue was purified by thin layer chromatography (eluent, hexane:ethyl acetate=5:1)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1.63 g (0.017 mol) of ethoxyamine hydrochloride and 1.15 g (0.0085 mol) of finely pulverulent potassium carbonate were stirred for 1 hour in 60 ml of dry methanol. 4.00 g (0.015 mol) of 2-chloro-3-formyl-4-methylsulfonylbenzoic acid in 40 ml of methanol were subsequently added. After the mixture was stirred for 12 hours at room temperature, the solvent was removed, the residue was taken up in ethyl acetate, and the organic phase was washed four times with water. After the mixture had been dried and the solvent distilled off, 3.60 g of 2-chloro-3-ethoxyiminomethyl-4-methylsulfonylbenzoic acid were obtained (78% yield). the solvent was removed the organic phase was washed four times with water After the mixture had been dried the solvent distilled off

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A suspension of 10.0 g. (0.046 mole) of 2,6-dinitro-4-methylchlorobenzene in 100 ml. of methanol was prepared, and to the suspension there was added 7.6 g. (0.092 mole) of ethoxyamine hydrochloride, and 13.9 g. (0.138 mole) of triethylamine. The reaction mixture was stirred for about 30 minutes at room temperature and then heated and stirred for about 30 minutes at about 50° C., after which an additional 16.7 g. (0.20 mole) of ethoxyamine hydrochloride was added, and the reaction mixture was stirred and refluxed for about 24 hours. An NMR spectrum of the reaction mixture indicated the presence of the desired product in about 70 percent yield. The reaction product mixture was poured over a mixture of ice and water, and the aqueous mixture filtered. The solid obtained was recrystallized from petroleum ether (b.p. 60°-71° C.) to yield 5.5 g. of product having a melting point of about 64°-66° C. The product was identified by its NMR spectrum as 2,6-dinitro-N-ethoxy-p-toluidine. A suspension of 10.0 g to the suspension there was added 7.6 g heated stirred for about 30 minutes at about 50° C. the reaction mixture was stirred refluxed for about 24 hours

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Following the procedure of Example 29, N-[2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)phenyl]ethoxyamine is prepared from 4-(2-chloro-4-trifluoromethylphenoxy)1,2-dinitrobenzene and ethoxyamine hydrochloride. The resulting N-phenylethoxyamine is then reacted with methyl bromoacetate, following the methods of this example, to yield N-methoxycarbonylmethyl-N-[2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)phenyl]ethoxyamine.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Following the procedure of Example 7 except substituting 1-bromopentane for 1-bromononane, ethoxylamine hydrochloride for methoxylamine hydrochloride and ethyl-3 iodovalerate for ethyl-4-iodobutyrate, and eliminating the addition of dicyclohexylamine, the title compound is obtained.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Following the procedure of Example 12 except substituting 1-hexenylcarboxylic acid for 1-decenylcarboxylic acid, ethoxylamine hydrochloride for methoxylamine hydrochloride and ethyl-3 iodovalerate for ethyl-4-iodobutyrate, and eliminating the addition of dicyclohexylamine, the title compound is obtained.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Ethoxyamine hydrochloride (0.3 g) and then aqueous sodium hydroxide (0.12 g in 1 ml of water) were added to a solution of 2-butyryl-3-hydroxy-5-(2-methyl-5-thiazolyl)cyclohex-2-en-1-one (0.7 g) in ethanol (50 ml) at 20° C. with stirring. After 20 hours, the mixture was diluted with water (200 ml) and then extracted with chloroform (2×100 ml). The dried (MgSO4) organic extract was evaporated to give 2-[1-ethoxyimino)butyl]-3-hydroxy-5-(2-methyl-5-thiazolyl)cyclohex-2-en-1-one (0.75 g, 95%) as a nearly colourless oil which was characterised by proton magnetic resonance spectroscopy (CDCl3 ; δ in ppm); 0.96 (3H, t); 1.31 (3H, t); 1.7 (2H, m); 2.65 (3H, s); 2.5-3.8 (7H, m); 4.10 (2H, q); 7.37 (1H, s); 15.1 (1H, brs). extracted with chloroform (2×100 ml) The dried (MgSO4) organic extract was evaporated