4-chloroheptane-3,5-dione

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

Procedure: Potassium carbonate (1.9 g, 14 mmol) was added to a solution of 3,5-dibromobenzenethiol (2.84 g, 10.5 mmol) (Preparation 48) and 4-chloroheptane-3,5-dione (1.7 g, 10.5 mmol) (Preparation 40) in acetone (12 ml) producing a white suspension. The mixture was stirred at room temperature for 15 hours. The mixture was concentrated under reduced pressure and the residue was partitioned between dichloromethane (100 ml) and 1N hydrochloric acid (70 ml). The aqueous layer was extracted with further dichloromethane (2×100 ml). The combined organic layers were washed with brine (50 ml), dried over magnesium sulphate, filtered and concentrated under reduced pressure to leave a pink oil. The crude product was purified by flash chromatography on silica gel eluting with pentane:dichloromethane (1:1, by volume) to provide the title compound (3 g) as a pink oil. producing a white suspension The mixture was concentrated under reduced pressure the residue was partitioned between dichloromethane (100 ml) and 1N hydrochloric acid (70 ml) The aqueous layer was extracted with further dichloromethane (2×100 ml) The combined organic layers were washed with brine (50 ml) dried over magnesium sulphate filtered concentrated under reduced pressure to leave a pink oil The crude product was purified by flash chromatography on silica gel eluting with pentane:dichloromethane (1:1, by volume)

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

Procedure: Chlorotrimethylsilane (29.7 ml, 0.234 mol) was added dropwise to a stirred pale yellow solution of tetrabutylammonium bromide (1.26 g, 3.9 mmol) in dry acetonitrile (116 ml) at room temperature under nitrogen. The resulting solution was cooled in ice and 3,5-heptanedione (10.6 ml, 78.0 mmol) and then dry dimethylsulphoxide (16.6 ml, 0.234 mol) were added dropwise over 5 minutes producing a yellow solution which was allowed to warm slowly to room temperature, with stirring, over 4 hours. The mixture was diluted with water (1 litre), stirred for 10 min and then extracted with ether (1×500 ml, 2×250 ml). The combined ether layers were dried over magnesium sulphate, filtered and concentrated under reduced pressure to leave a yellow oil. The crude product was purified by distillation under reduced pressure to afford the title compound (5.5 g) as a pale yellow oil, b.p. 102-105° C./54 mmHg containing ca. 10% 4,4-dichloro-3,5-heptanedione as estimated by microanalysis. The resulting solution was cooled in ice producing a yellow solution which stirred for 10 min extracted with ether (1×500 ml, 2×250 ml) The combined ether layers were dried over magnesium sulphate filtered concentrated under reduced pressure to leave a yellow oil The crude product was purified by distillation under reduced pressure

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

Procedure: Potassium carbonate (1.9 g, 14 mmol) was added to a solution of 3,5-dibromobenzenethiol (2.84 g, 10.5 mmol) (Preparation 48) and 4-chloroheptane-3,5-dione (1.7 g, 10.5 mmol) (Preparation 40) in acetone (12 ml) producing a white suspension. The mixture was stirred at room temperature for 15 hours. The mixture was concentrated under reduced pressure and the residue was partitioned between dichloromethane (100 ml) and 1N hydrochloric acid (70 ml). The aqueous layer was extracted with further dichloromethane (2×100 ml). The combined organic layers were washed with brine (50 ml), dried over magnesium sulphate, filtered and concentrated under reduced pressure to leave a pink oil. The crude product was purified by flash chromatography on silica gel eluting with pentane:dichloromethane (1:1, by volume) to provide the title compound (3 g) as a pink oil. producing a white suspension The mixture was concentrated under reduced pressure the residue was partitioned between dichloromethane (100 ml) and 1N hydrochloric acid (70 ml) The aqueous layer was extracted with further dichloromethane (2×100 ml) The combined organic layers were washed with brine (50 ml) dried over magnesium sulphate filtered concentrated under reduced pressure to leave a pink oil The crude product was purified by flash chromatography on silica gel eluting with pentane:dichloromethane (1:1, by volume)

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

Procedure: Potassium carbonate (1.9 g, 14 mmol) was added to a solution of 3,5-dibromobenzenethiol (2.84 g, 10.5 mmol) (Preparation 48) and 4-chloroheptane-3,5-dione (1.7 g, 10.5 mmol) (Preparation 40) in acetone (12 ml) producing a white suspension. The mixture was stirred at room temperature for 15 hours. The mixture was concentrated under reduced pressure and the residue was partitioned between dichloromethane (100 ml) and 1N hydrochloric acid (70 ml). The aqueous layer was extracted with further dichloromethane (2×100 ml). The combined organic layers were washed with brine (50 ml), dried over magnesium sulphate, filtered and concentrated under reduced pressure to leave a pink oil. The crude product was purified by flash chromatography on silica gel eluting with pentane:dichloromethane (1:1, by volume) to provide the title compound (3 g) as a pink oil. producing a white suspension The mixture was concentrated under reduced pressure the residue was partitioned between dichloromethane (100 ml) and 1N hydrochloric acid (70 ml) The aqueous layer was extracted with further dichloromethane (2×100 ml) The combined organic layers were washed with brine (50 ml) dried over magnesium sulphate filtered concentrated under reduced pressure to leave a pink oil The crude product was purified by flash chromatography on silica gel eluting with pentane:dichloromethane (1:1, by volume)

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

Procedure: Chlorotrimethylsilane (29.7 ml, 0.234 mol) was added dropwise to a stirred pale yellow solution of tetrabutylammonium bromide (1.26 g, 3.9 mmol) in dry acetonitrile (116 ml) at room temperature under nitrogen. The resulting solution was cooled in ice and 3,5-heptanedione (10.6 ml, 78.0 mmol) and then dry dimethylsulphoxide (16.6 ml, 0.234 mol) were added dropwise over 5 minutes producing a yellow solution which was allowed to warm slowly to room temperature, with stirring, over 4 hours. The mixture was diluted with water (1 liter), stirred for 10 min and then extracted with ether (1×500 ml, 2×250 ml). The combined ether layers were dried over magnesium sulphate, filtered and concentrated under reduced pressure to leave a yellow oil. The crude product was purified by distillation under reduced pressure to afford the title compound (5.5 g) as a pale yellow oil, b.p. 102–105° C./54 mmHg containing ca. 10% 4,4-dichloro-3,5-heptanedione as estimated by microanalysis. The resulting solution was cooled in ice producing a yellow solution which stirred for 10 min extracted with ether (1×500 ml, 2×250 ml) The combined ether layers were dried over magnesium sulphate filtered concentrated under reduced pressure to leave a yellow oil The crude product was purified by distillation under reduced pressure

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

Procedure: Chlorotrimethylsilane (29.7 ml, 0.234 mol) was added dropwise to a stirred pale yellow solution of tetrabutylammonium bromide (1.26 g, 3.9 mmol) in dry acetonitrile (116 ml) at room temperature under nitrogen. The resulting solution was cooled in ice and 3,5-heptanedione (10.6 ml, 78.0 mmol) and then dry dimethylsulphoxide (16.6 ml, 0.234 mol) were added dropwise over 5 minutes producing a yellow solution which was allowed to warm slowly to room temperature, with stirring, over 4 hours. The mixture was diluted with water (1 liter), stirred for 10 min and then extracted with ether (1×500 ml, 2×250 ml). The combined ether layers were dried over magnesium sulphate, filtered and concentrated under reduced pressure to leave a yellow oil. The crude product was purified by distillation under reduced pressure to afford the title compound (5.5 g) as a pale yellow oil, b.p. 102–105° C./54 mmHg containing ca. 10% 4,4-dichloro-3,5-heptanedione as estimated by microanalysis. The resulting solution was cooled in ice producing a yellow solution which stirred for 10 min extracted with ether (1×500 ml, 2×250 ml) The combined ether layers were dried over magnesium sulphate filtered concentrated under reduced pressure to leave a yellow oil The crude product was purified by distillation under reduced pressure

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

Procedure: Chlorotrimethylsilane (29.7 ml, 0.234 mol) was added dropwise to a stirred pale yellow solution of tetrabutylammonium bromide (1.26 g, 3.9 mmol) in dry acetonitrile (16 ml) at room temperature under nitrogen. The resulting solution was cooled in ice and 3,5-heptanedione (10.6 ml, 78.0 mmol) and then dry dimethylsulphoxide (16.6 ml, 0.234 mol) were added dropwise over 5 minutes producing a yellow solution which was allowed to warm slowly to room temperature, with stirring, over 4 hours. The mixture was diluted with water (litre), stirred for 10 min and then extracted with ether (1×500 ml, 2×250 ml). The combined ether layers were dried over magnesium sulphate, filtered and concentrated under reduced pressure to leave a yellow oil. The crude product was purified by distillation under reduced pressure to afford the title compound (5.5 g) as a pale yellow oil, b.p. 102-105° C./54 mmHg containing ca. 10% 4,4-dichloro-3,5-heptanedione as estimated by microanalysis. The resulting solution was cooled in ice producing a yellow solution which stirred for 10 min extracted with ether (1×500 ml, 2×250 ml) The combined ether layers were dried over magnesium sulphate filtered concentrated under reduced pressure to leave a yellow oil The crude product was purified by distillation under reduced pressure

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

Procedure: Chlorotrimethylsilane (29.7 ml, 0.234 mol) was added dropwise to a stirred pale yellow solution of tetrabutylammonium bromide (1.26 g, 3.9 mmol) in dry acetonitrile (16 ml) at room temperature under nitrogen. The resulting solution was cooled in ice and 3,5-heptanedione (10.6 ml, 78.0 mmol) and then dry dimethylsulphoxide (16.6 ml, 0.234 mol) were added dropwise over 5 minutes producing a yellow solution which was allowed to warm slowly to room temperature, with stirring, over 4 hours. The mixture was diluted with water (litre), stirred for 10 min and then extracted with ether (1×500 ml, 2×250 ml). The combined ether layers were dried over magnesium sulphate, filtered and concentrated under reduced pressure to leave a yellow oil. The crude product was purified by distillation under reduced pressure to afford the title compound (5.5 g) as a pale yellow oil, b.p. 102-105° C./54 mmHg containing ca. 10% 4,4-dichloro-3,5-heptanedione as estimated by microanalysis. The resulting solution was cooled in ice producing a yellow solution which stirred for 10 min extracted with ether (1×500 ml, 2×250 ml) The combined ether layers were dried over magnesium sulphate filtered concentrated under reduced pressure to leave a yellow oil The crude product was purified by distillation under reduced pressure

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

Procedure: Potassium carbonate (1.9 g, 14 mmol) was added to a solution of 3,5-dibromobenzenethiol (2.84 g, 10.5 mmol) (Preparation 48) and 4-chloroheptane-3,5-dione (1.7 g, 10.5 mmol) (Preparation 40) in acetone (12 ml) producing a white suspension. The mixture was stirred at room temperature for 15 hours. The mixture was concentrated under reduced pressure and the residue was partitioned between dichloromethane (100 ml) and 1N hydrochloric acid (70 ml). The aqueous layer was extracted with further dichloromethane (2×100 ml). The combined organic layers were washed with brine (50 ml), dried over magnesium sulphate, filtered and concentrated under reduced pressure to leave a pink oil. The crude product was purified by flash chromatography on silica gel eluting with pentane:dichloromethane (1:1, by volume) to provide the title compound (3 g) as a pink oil. producing a white suspension The mixture was concentrated under reduced pressure the residue was partitioned between dichloromethane (100 ml) and 1N hydrochloric acid (70 ml) The aqueous layer was extracted with further dichloromethane (2×100 ml) The combined organic layers were washed with brine (50 ml) dried over magnesium sulphate filtered concentrated under reduced pressure to leave a pink oil The crude product was purified by flash chromatography on silica gel eluting with pentane:dichloromethane (1:1, by volume)

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

Procedure: Chlorotrimethylsilane (29.7 ml, 0.234 mol) was added dropwise to a stirred pale yellow solution of tetrabutylammonium bromide (1.26 g, 3.9 mmol) in dry acetonitrile (116 ml) at room temperature under nitrogen. The resulting solution was cooled in ice and 3,5-heptanedione (10.6 ml, 78.0 mmol) and then dry dimethylsulphoxide (16.6 ml, 0.234 mol) were added dropwise over 5 minutes producing a yellow solution which was allowed to warm slowly to room temperature, with stirring, over 4 hours. The mixture was diluted with water (1 litre), stirred for 10 min and then extracted with ether (1×500 ml, 2×250 ml). The combined ether layers were dried over magnesium sulphate, filtered and concentrated under reduced pressure to leave a yellow oil. The crude product was purified by distillation under reduced pressure to afford the title compound (5.5 g) as a pale yellow oil, b.p. 102-105° C./54 mmHg containing ca. 10% 4,4-dichloro-3,5-heptanedione as estimated by microanalysis. The resulting solution was cooled in ice producing a yellow solution which stirred for 10 min extracted with ether (1×500 ml, 2×250 ml) The combined ether layers were dried over magnesium sulphate filtered concentrated under reduced pressure to leave a yellow oil The crude product was purified by distillation under reduced pressure

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

Procedure: Chlorotrimethylsilane (29.7 ml, 0.234 mol) was added dropwise to a stirred pale yellow solution of tetrabutylammonium bromide (1.26 g, 3.9 mmol) in dry acetonitrile (116 ml) at room temperature under nitrogen. The resulting solution was cooled in ice and 3,5-heptanedione (10.6 ml, 78.0 mmol) and then dry dimethylsulphoxide (16.6 ml, 0.234 mol) were added dropwise over 5 minutes producing a yellow solution which was allowed to warm slowly to room temperature, with stirring, over 4 hours. The mixture was diluted with water (1 litre), stirred for 10 min and then extracted with ether (1×500 ml, 2×250 ml). The combined ether layers were dried over magnesium sulphate, filtered and concentrated under reduced pressure to leave a yellow oil. The crude product was purified by distillation under reduced pressure to afford the title compound (5.5 g) as a pale yellow oil, b.p. 102-105° C./54 mmHg containing ca. 10% 4,4-dichloro-3,5-heptanedione as estimated by microanalysis. The resulting solution was cooled in ice producing a yellow solution which stirred for 10 min extracted with ether (1×500 ml, 2×250 ml) The combined ether layers were dried over magnesium sulphate filtered concentrated under reduced pressure to leave a yellow oil The crude product was purified by distillation under reduced pressure

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

Procedure: Chlorotrimethylsilane (29.7 ml, 0.234 mol) was added dropwise to a stirred pale yellow solution of tetrabutylammonium bromide (1.26 g, 3.9 mmol) in dry acetonitrile (116 ml) at room temperature under nitrogen. The resulting solution was cooled in ice and 3,5-heptanedione (10.6 ml, 78.0 mmol) and then dry dimethylsulphoxide (16.6 ml, 0.234 mol) were added dropwise over 5 minutes producing a yellow solution which was allowed to warm slowly to room temperature, with stirring, over 4 hours. The mixture was diluted with water (1 liter), stirred for 10 min and then extracted with ether (1×500 ml, 2×250 ml). The combined ether layers were dried over magnesium sulphate, filtered and concentrated under reduced pressure to leave a yellow oil. The crude product was purified by distillation under reduced pressure to afford the title compound (5.5 g) as a pale yellow oil, b.p. 102–105° C./54 mmHg containing ca. 10% 4,4-dichloro-3,5-heptanedione as estimated by microanalysis. The resulting solution was cooled in ice producing a yellow solution which stirred for 10 min extracted with ether (1×500 ml, 2×250 ml) The combined ether layers were dried over magnesium sulphate filtered concentrated under reduced pressure to leave a yellow oil The crude product was purified by distillation under reduced pressure