O-(3-chloroprop-2-enyl)hydroxylamine;hydrochloride

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

Procedure: 0.38 g of sodium methoxide, 10 ml of methanol, and 1.0 g of 3-chloroallyloxyamine hydrochloride (H2NOCH2CH=CHCl) were admixed together and then stirred for 10 minutes at room temperature. 2 g of 2-butyryl-5-(2-ethylthiopropyl)cyclohexane-1,3-dione was added and the resulting mixture stirred for about two days at room temperature. The mixture was then concentrated by evaporation and the concentrate mixed with 60 ml of diethyl ether and 40 ml of water. The ether layer was extracted with 40 ml of aqueous 2 wt. % sodium hydroxide solution, washed with 20 ml of water, dried over anhydrous magnesium sulfate and evaporated affording a minor amount of the title compound as the trans isomer. the resulting mixture stirred for about two days at room temperature The mixture was then concentrated by evaporation the concentrate mixed with 60 ml of diethyl ether and 40 ml of water The ether layer was extracted with 40 ml of aqueous 2 wt. % sodium hydroxide solution washed with 20 ml of water dried over anhydrous magnesium sulfate evaporated

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

Procedure: 10.2 parts by weight of 2-butyryl-5-(3-methyl-4-ethyl-6-isobutoxytetrahydropyran-2-yl)-cyclohexane-1,3-dione were dissolved in 100 parts by volume of ethanol, and 2.42 parts by weight of sodium acetate and 3.86 parts by weight of O-(3-chloroallyl)-hydroxylamine hydrochloride were added. The mixture was stirred for several hours at room temperature and then poured into ice-water, and the resulting mixture was extracted with methylene chloride. The methylene chloride phase was evaporated off, leaving 11.1 parts by weight of 2-(3-chloroallyloxyaminobutylidene)-5-(3-methyl-4-ethyl-6-isobutoxytetrahydropyran-2-yl)-cyclohexane-1,3-dione as a yellow oil of refractive index nD22 1.5129. were added the resulting mixture was extracted with methylene chloride The methylene chloride phase was evaporated off

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

Procedure: 10.2 parts by weight of 2-butyryl-5-(3-methyl-4-ethyl-6-isobutoxytetrahydropyran-2-yl)-cyclohexane-1,3-dione were dissolved in 100 parts by volume of ethanol, and 2.42 parts by weight of sodium acetate and 3.86 parts by weight of O-(3-chloroallyl)-hydroxylamine hydrochloride were added. The mixture was stirred for several hours at room temperature and then poured into ice-water, and the resulting mixture was extracted with methylene chloride. The methylene chloride phase was evaporated off, leaving 11.1 parts by weight of 2-(3-chloroallyloxyaminobutylidene)-5-(3-methyl-4-ethyl-6-isobutoxytetrahydropyran-2-yl)-cyclohexane-1,3-dione as a yellow oil of refractive index nD22 1.5129. were added the resulting mixture was extracted with methylene chloride The methylene chloride phase was evaporated off

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

Procedure: 2-[1-(3-Chloroallyloxyimino)butyl]-3-hydroxy-5-(4,6-dimethoxy-2-methylthio-5-pyrimidyl)cyclohex-2-en-1-one (6) was prepared from 2-butyryl-3-hydroxy-5-[5-(4,6-dimethoxy-2-methylthiopyrimidyl]cyclohex-2-en-1-one (see Example 3) and 3-chloroallyloxyamine hydrochloride following essentially the same procedure as that described in Example 1, part (iv). The product was obtained as a nearly colourless oil and was characterized by nuclear resonance spectroscopy. The product was obtained as a nearly colourless oil

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

Procedure: 2-[1-(3-Chloroallyloxyimino)butyl]-3-hydroxy-5-(4,6-dimethoxy-2-methylthio-5-pyrimidyl)cyclohex-2-en-1-one (6) was prepared from 2-butyryl-3-hydroxy-5-[5-(4,6-dimethoxy-2-methylthiopyrimidyl]cyclohex-2-en-1-one (see Example 3) and 3-chloroallyloxyamine hydrochloride following essentially the same procedure as that described in Example 1, part (iv). The product was obtained as a nearly colourless oil and was characterized by nuclear resonance spectroscopy. The product was obtained as a nearly colourless oil

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

Procedure: 0.38 g of sodium methoxide, 10 ml of methanol, and 1.0 g of 3-chloroallyloxyamine hydrochloride (H2NOCH2CH=CHCl) were admixed together and then stirred for 10 minutes at room temperature. 2 g of 2-butyryl-5-(2-ethylthiopropyl)cyclohexane-1,3-dione was added and the resulting mixture stirred for about two days at room temperature. The mixture was then concentrated by evaporation and the concentrate mixed with 60 ml of diethyl ether and 40 ml of water. The ether layer was extracted with 40 ml of aqueous 2 wt. % sodium hydroxide solution, washed with 20 ml of water, dried over anhydrous magnesium sulfate and evaporated affording a minor amount of the title compound as the trans isomer. the resulting mixture stirred for about two days at room temperature The mixture was then concentrated by evaporation the concentrate mixed with 60 ml of diethyl ether and 40 ml of water The ether layer was extracted with 40 ml of aqueous 2 wt. % sodium hydroxide solution washed with 20 ml of water dried over anhydrous magnesium sulfate evaporated

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

Procedure: 0.38 g of sodium methoxide, 10 ml of methanol, and 1.0 g of 3-chloroallyloxyamine hydrochloride (H2NOCH2CH=CHCl) were admixed together and then stirred for 10 minutes at room temperature. 2 g of 2-butyryl-5-(2-ethylthiopropyl)cyclohexane-1,3-dione was added and the resulting mixture stirred for about two days at room temperature. The mixture was then concentrated by evaporation and the concentrate mixed with 60 ml of diethyl ether and 40 ml of water. The ether layer was extracted with 40 ml of aqueous 2 wt. % sodium hydroxide solution, washed with 20 ml of water, dried over anhydrous magnesium sulfate and evaporated affording a minor amount of the title compound as the trans isomer. the resulting mixture stirred for about two days at room temperature The mixture was then concentrated by evaporation the concentrate mixed with 60 ml of diethyl ether and 40 ml of water The ether layer was extracted with 40 ml of aqueous 2 wt. % sodium hydroxide solution washed with 20 ml of water dried over anhydrous magnesium sulfate evaporated

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

Procedure: 3-Chloroallyloxyamine hydrochloride (0.3 g) and then anhydrous sodium acetate (0.2 g) were added to a solution of 3-hydroxy-5-(3-crotonyl-2,4,6-trimethylphenyl)-2-propionylcyclohex-2-en-1-one (0.7 g) in anhydrous ethanol (80 ml). The mixture was stirred briefly then allowed to stand at room temperature for 16 hours. The ethanol was removed by evaporation under reduced pressure using a rotary evaporator. The residue was treated with chloroform and the organic phase was washed twice with water (50 ml). The chloroform layer was dried over magnesium sulphate and the solvent was removed by evaporation under reduced pressure to give the product 2-[1-(3-chloroallyloxyimino)propyl]-3-hydroxy-5-(3-crotonyl-2,4,6-trimethylphenyl)cyclohex-2-en-1-one (0.7 g, 85%) as a colourless oil. Proton magnetic spectrum (CDCl3 ; δ in ppm); 1.19 (3H, t); 1.92 (3H, d, J=7 Hz); 2.09 (3H, s); 2.19 (3H, s); 2.39 (3H, s); 2.2-4.0 (7H, m); 4.4-4.8 (2H, m); 5.86.7 (4H, m); 6.86 (1H, s); 15.2 (1 H, bs). The ethanol was removed by evaporation under reduced pressure a rotary evaporator The residue was treated with chloroform the organic phase was washed twice with water (50 ml) The chloroform layer was dried over magnesium sulphate the solvent was removed by evaporation under reduced pressure

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

Procedure: 10.2 parts by weight of 2-butyryl-5-(3-methyl-4-ethyl-6-isobutoxytetrahydropyran-2-yl)-cyclohexane-1,3-dione were dissolved in 100 parts by volume of ethanol, and 2.42 parts by weight of sodium acetate and 3.86 parts by weight of O-(3-chloroallyl)-hydroxylamine hydrochloride were added. The mixture was stirred for several hours at room temperature and then poured into ice-water, and the resulting mixture was extracted with methylene chloride. The methylene chloride phase was evaporated off, leaving 11.1 parts by weight of 2-(3-chloroallyloxyaminobutylidene)-5-(3-methyl-4-ethyl-6-isobutoxytetrahydropyran-2-yl)-cyclohexane-1,3-dione as a yellow oil of refractive index nD22 1.5129. were added the resulting mixture was extracted with methylene chloride The methylene chloride phase was evaporated off

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

Procedure: 2-[1-(3-Chloroallyloxyimino)butyl]-3-hydroxy-5-(4,6-dimethoxy-2-methylthio-5-pyrimidyl)cyclohex-2-en-1-one (6) was prepared from 2-butyryl-3-hydroxy-5-[5-(4,6-dimethoxy-2-methylthiopyrimidyl]cyclohex-2-en-1-one (see Example 3) and 3-chloroallyloxyamine hydrochloride following essentially the same procedure as that described in Example 1, part (iv). The product was obtained as a nearly colourless oil and was characterized by nuclear resonance spectroscopy. The product was obtained as a nearly colourless oil

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

Procedure: 0.38 g of sodium methoxide, 10 ml of methanol, and 1.0 g of 3-chloroallyloxyamine hydrochloride (H2NOCH2CH=CHCl) were admixed together and then stirred for 10 minutes at room temperature. 2 g of 2-butyryl-5-(2-ethylthiopropyl)cyclohexane-1,3-dione was added and the resulting mixture stirred for about two days at room temperature. The mixture was then concentrated by evaporation and the concentrate mixed with 60 ml of diethyl ether and 40 ml of water. The ether layer was extracted with 40 ml of aqueous 2 wt. % sodium hydroxide solution, washed with 20 ml of water, dried over anhydrous magnesium sulfate and evaporated affording a minor amount of the title compound as the trans isomer. the resulting mixture stirred for about two days at room temperature The mixture was then concentrated by evaporation the concentrate mixed with 60 ml of diethyl ether and 40 ml of water The ether layer was extracted with 40 ml of aqueous 2 wt. % sodium hydroxide solution washed with 20 ml of water dried over anhydrous magnesium sulfate evaporated