1,4-氧杂环丁烷

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A stirred solution of 3,4-dichlorophenylmagnesium bromide [prepared from 3,4-dichlorobromobenzene (10.2 g, 45 mmol) and magnesium (1.1 g, 45 mmol) in the usual fashion] was treated with a solution of 3-chloro-1,4-oxathiane [prepared from 1,4-oxathiane (2.6 g, 25 mmol) using the method of Tuleen and Bennet J. Het. Chem. 1969, 6, 115] in benzene (30 ml), maintaining the temperature of reaction below 10° C. The mixture was allowed to stand at room temperature overnight. It was then poured into ammonium chloride solution (50 ml), the organic phase was separated and the aqueous washed with ether (2×40 ml). The combined organic extracts were dried (MgSO4) and purified by flash chromatography on silica eluting with toluene/hexane (1:1) to give 3-(3,4-dichlorophenyl)-1,4-oxathiane (4.5 g), as colourless crystals, m.p. 65°-68° C.; the temperature of reaction below 10° C the organic phase was separated the aqueous washed with ether (2×40 ml) The combined organic extracts were dried (MgSO4) purified by flash chromatography on silica eluting with toluene/hexane (1:1)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A stirred solution of 3,4-dichlorophenylmagnesium bromide [prepared from 3,4-dichlorobromobenzene (10.2 g, 45 mmol) and magnesium (1.1 g, 45 mmol) in the usual fashion] was treated with a solution of 3-chloro-1,4-oxathiane [prepared from 1,4-oxathiane (2.6 g, 25 mmol) using the method of Tuleen and Bennet J. Het. Chem. 1969, 6, 115] in benzene (30 ml), maintaining the temperature of reaction below 10° C. The mixture was allowed to stand at room temperature overnight. It was then poured into ammonium chloride solution (50 ml), the organic phase was separated and the aqueous washed with ether (2×40 ml). The combined organic extracts were dried (MgSO4) and purified by flash chromatography on silica eluting with toluene/hexane (1:1) to give 3-(3,4-dichlorophenyl)-1,4-oxathiane (4.5 g), as colourless crystals, m.p. 65°-68° C.; the temperature of reaction below 10° C the organic phase was separated the aqueous washed with ether (2×40 ml) The combined organic extracts were dried (MgSO4) purified by flash chromatography on silica eluting with toluene/hexane (1:1)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A stirred solution of 3,4-dichlorophenylmagnesium bromide [prepared from 3,4-dichlorobromobenzene (10.2 g, 45 mmol) and magnesium (1.1 g, 45 mmol) in the usual fashion] was treated with a solution of 3-chloro-1,4-oxathiane [prepared from 1,4-oxathiane (2.6 g, 25 mmol) using the method of Tuleen and Bennet J. Het. Chem. 1969, 6, 115] in benzene (30 ml), maintaining the temperature of reaction below 10° C. The mixture was allowed to stand at room temperature overnight. It was then poured into ammonium chloride solution (50 ml), the organic phase was separated and the aqueous washed with ether (2×40 ml). The combined organic extracts were dried (MgSO4) and purified by flash chromatography on silica eluting with toluene/hexane (1:1) to give 3-(3,4-dichlorophenyl)-1,4-oxathiane (4.5 g), as colourless crystals, m.p. 65°-68° C.; the temperature of reaction below 10° C the organic phase was separated the aqueous washed with ether (2×40 ml) The combined organic extracts were dried (MgSO4) purified by flash chromatography on silica eluting with toluene/hexane (1:1)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A stirred solution of 3,4-dichlorophenylmagnesium bromide [prepared from 3,4-dichlorobromobenzene (10.2 g, 45 mmol) and magnesium (1.1 g, 45 mmol) in the usual fashion] was treated with a solution of 3-chloro-1,4-oxathiane [prepared from 1,4-oxathiane (2.6 g, 25 mmol) using the method of Tuleen and Bennet J. Het. Chem. 1969, 6, 115] in benzene (30 ml), maintaining the temperature of reaction below 10° C. The mixture was allowed to stand at room temperature overnight. It was then poured into ammonium chloride solution (50 ml), the organic phase was separated and the aqueous washed with ether (2×40 ml). The combined organic extracts were dried (MgSO4) and purified by flash chromatography on silica eluting with toluene/hexane (1:1) to give 3-(3,4-dichlorophenyl)-1,4-oxathiane (4.5 g), as colourless crystals, m.p. 65°-68° C.; the temperature of reaction below 10° C the organic phase was separated the aqueous washed with ether (2×40 ml) The combined organic extracts were dried (MgSO4) purified by flash chromatography on silica eluting with toluene/hexane (1:1)

反应条件: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 1,4-Thioxane (0.02 g) and N,N-diisopropylethylamine (0.04 ml) were added to a solution of Intermediate 10 (0.08 g) in dichloromethane (2 ml). The mixture was stirred at 23° C. for 16 h, and the solvent evaporated in vacuo. The residue was dissolved in dichloromethane (3 ml), and the solution shaken with polystyrene methyl isocyanate resin (Argonaut Technologies, 0.14 g, 1.45 mmol/g) for 2 h. The solution was drained from the resin, and the resin washed with dichloromethane (6 ml) and methanol (3 ml); the combined filtrate and washings were concentrated in vacuo. The residue was purified further by solid phase extraction (Isolute SCX sulphonic acid column), eluting with methanol followed by 10% 0.880 ammonia solution in methanol, to give the title compound as a pale yellow gum (0.065 g). the solvent evaporated in vacuo The residue was dissolved in dichloromethane (3 ml) the solution shaken with polystyrene methyl isocyanate resin (Argonaut Technologies, 0.14 g, 1.45 mmol/g) for 2 h the resin washed with dichloromethane (6 ml) and methanol (3 ml) the combined filtrate and washings were concentrated in vacuo The residue was purified further by solid phase extraction (Isolute SCX sulphonic acid column) eluting with methanol

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A stirred solution of 3,4-dichlorophenylmagnesium bromide [prepared from 3,4-dichlorobromobenzene (10.2 g, 45 mmol) and magnesium (1.1 g, 45 mmol) in the usual fashion] was treated with a solution of 3-chloro-1,4-oxathiane [prepared from 1,4-oxathiane (2.6 g, 25 mmol) using the method of Tuleen and Bennet J. Het. Chem. 1969, 6, 115] in benzene (30 ml), maintaining the temperature of reaction below 10° C. The mixture was allowed to stand at room temperature overnight. It was then poured into ammonium chloride solution (50 ml), the organic phase was separated and the aqueous washed with ether (2×40 ml). The combined organic extracts were dried (MgSO4) and purified by flash chromatography on silica eluting with toluene/hexane (1:1) to give 3-(3,4-dichlorophenyl)-1,4-oxathiane (4.5 g), as colourless crystals, m.p. 65°-68° C.; the temperature of reaction below 10° C the organic phase was separated the aqueous washed with ether (2×40 ml) The combined organic extracts were dried (MgSO4) purified by flash chromatography on silica eluting with toluene/hexane (1:1)