1,3,5-Trichloro-2-iodobenzene

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Add 1-iodo-2,4,6-trichlorobenzene (1500 mg, 4.88 mmol), zinc cyanide (345 mg, 2.94 mmol) and tetrakis(triphenylphosphine)palladium(0) (282 mg, 0.244 mmol) to anhydrous DMF (30 mL). Heat to 85° C. overnight. Cool to room temperature, dilute with toluene, wash with 2 N ammonium hydroxide (3×) and saturated aqueous sodium chloride and concentrate. Purify by silica gel chromatography, eluting with hexanes/dichloromethane to give 2,4,6-trichlorobenzonitrile (850 mg, 84%): 1H NMR (400 MHz, CDCl3) δ 7.76 (s, 1H), 7.65 (s, 1H). Cool to room temperature wash with 2 N ammonium hydroxide (3×) and saturated aqueous sodium chloride concentrate Purify by silica gel chromatography eluting with hexanes/dichloromethane

反応条件: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Add 1-iodo-2,4,6-trichlorobenzene (1500 mg, 4.88 mmol), zinc cyanide (345 mg, 2.94 mmol) and tetrakis(triphenylphosphine)palladium(0) (282 mg, 0.244 mmol) to anhydrous DMF (30 mL). Heat to 85° C. overnight. Cool to room temperature, dilute with toluene, wash with 2 N ammonium hydroxide (3×) and saturated aqueous sodium chloride and concentrate. Purify by silica gel chromatography, eluting with hexanes/dichloromethane to give 2,4,6-trichlorobenzonitrile (850 mg, 84%): 1H NMR (400 MHz, CDCl3) δ 7.76 (s, 1H), 7.65 (s, 1H). Cool to room temperature wash with 2 N ammonium hydroxide (3×) and saturated aqueous sodium chloride concentrate Purify by silica gel chromatography eluting with hexanes/dichloromethane

反応条件: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a microwave vial were added propargyl alcohol (0.19 ml; 3.3 mmol), 1,3,5-trichloro-2-iodo-benzene (0.50 g; 1.6 mmol), N,N-dimethylformamide (6 ml), triethylamine (4 ml), bis(triphenylphosphine) palladium(II) chloride (0.11 g; 0.16 mmol) and copper iodide (31 mg; 0.16 mmol). The mixture was degassed under argon. The orange solution was heated in the microwave at 120° C. during 25 min. The mixture obtained was poured in brine and extracted three times with dichloromethane. Organic were combined, dried over sodium sulfate and evaporated under reduced pressure to provide the crude which was subject to flash chromatography (eluant: c-hexane/ethyl acetate 8:2). 290 mg (75% of theory) of 3-(2,4,6-trichloro-phenyl)-prop-2-yn-1-ol was obtained as a yellow solid. The mixture was degassed under argon The mixture obtained extracted three times with dichloromethane dried over sodium sulfate evaporated under reduced pressure to provide the crude which

反応条件: temp:12.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of paratoluene sulfonic acid monohydrate (14.5 g; 76.4 mmol) in acetonitrile (100 ml) was added the 2,4,6-trichloroaniline (5.0 g; 25.5 mmol). The resulting white suspension was cooled to 10-15° C. and to this was added, gradually a solution of sodium nitrite (3.5 g; 51.0 mmol) and potassium iodide (10.6 g; 63.6 mmol) in water (15 ml), the suspension became dark brown, thick and gas release was observed. The thick mixture was stirred for 10 min at 10° C. and then temperature was allowed to increase to 20° C. The solution obtained was stirred for 1 h. The solution was poured in water, 1M sodium hydrogen carbonate solution was added (pH adjusted to 9-10) and 2M solution of sodium thiosulfate was added. The mixture was extracted three times with dichloromethane. Organics were combined, dried over sodium sulfate and the solvent was removed in vacuo to provide a resin which was subject to flash column chromatography (eluant: c-hexane). 6.3 g (80% of theory) of 1,3,5-trichloro-2-iodo-benzene was obtained as a white solid. to this was added to increase to 20° C The solution obtained was stirred for 1 h was added The mixture was extracted three times with dichloromethane dried over sodium sulfate the solvent was removed in vacuo to provide a resin which

反応条件: temp:12.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of paratoluene sulfonic acid monohydrate (14.5 g; 76.4 mmol) in acetonitrile (100 ml) was added the 2,4,6-trichloroaniline (5.0 g; 25.5 mmol). The resulting white suspension was cooled to 10-15° C. and to this was added, gradually a solution of sodium nitrite (3.5 g; 51.0 mmol) and potassium iodide (10.6 g; 63.6 mmol) in water (15 ml), the suspension became dark brown, thick and gas release was observed. The thick mixture was stirred for 10 min at 10° C. and then temperature was allowed to increase to 20° C. The solution obtained was stirred for 1 h. The solution was poured in water, 1M sodium hydrogen carbonate solution was added (pH adjusted to 9-10) and 2M solution of sodium thiosulfate was added. The mixture was extracted three times with dichloromethane. Organics were combined, dried over sodium sulfate and the solvent was removed in vacuo to provide a resin which was subject to flash column chromatography (eluant: c-hexane). 6.3 g (80% of theory) of 1,3,5-trichloro-2-iodo-benzene was obtained as a white solid. to this was added to increase to 20° C The solution obtained was stirred for 1 h was added The mixture was extracted three times with dichloromethane dried over sodium sulfate the solvent was removed in vacuo to provide a resin which

反応条件: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Add 1-iodo-2,4,6-trichlorobenzene (1500 mg, 4.88 mmol), zinc cyanide (345 mg, 2.94 mmol) and tetrakis(triphenylphosphine)palladium(0) (282 mg, 0.244 mmol) to anhydrous DMF (30 mL). Heat to 85° C. overnight. Cool to room temperature, dilute with toluene, wash with 2 N ammonium hydroxide (3×) and saturated aqueous sodium chloride and concentrate. Purify by silica gel chromatography, eluting with hexanes/dichloromethane to give 2,4,6-trichlorobenzonitrile (850 mg, 84%): 1H NMR (400 MHz, CDCl3) δ 7.76 (s, 1H), 7.65 (s, 1H). Cool to room temperature wash with 2 N ammonium hydroxide (3×) and saturated aqueous sodium chloride concentrate Purify by silica gel chromatography eluting with hexanes/dichloromethane

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A round bottom flask equipped with magnetic stirrer and nitrogen inlet was charged with but-3-en-2-one (1.14 g, 16.25 mmol), 1,3,5-trichloro-2-iodo-benzene (2.0 g, 6.5 mmol), Pd(OAc)2 (125 mg, 0.65 mmol), sodium hydrogen carbonate (1.64 g, 19.5 mmol) and tetrabutylammonium chloride (2.17 g, 7.8 mmol) in DMF (20 ml). The mixture was stirred at 50° C. for 24 hours. The reaction mixture was poured onto water (100 ml) and extracted with ether (3×50 ml). Combined organic layers were dried over anhydrous sodium sulphate, filtered and concentrated in vacuo. The residue was purified by flash chromatography over silica gel (150 g) (eluent: n-hexane/ethyl acetate 1:20) to afford 1.02 g (63% of theory) of (E)-4-(2,4,6-trichloro-phenyl)-but-3-en-2-one in form of an oil. A round bottom flask equipped with magnetic stirrer and nitrogen inlet The reaction mixture was poured onto water (100 ml) extracted with ether (3×50 ml) Combined organic layers were dried over anhydrous sodium sulphate filtered concentrated in vacuo The residue was purified by flash chromatography over silica gel (150 g) (eluent: n-hexane/ethyl acetate 1:20)

反応条件: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a microwave vial were added propargyl alcohol (0.19 ml; 3.3 mmol), 1,3,5-trichloro-2-iodo-benzene (0.50 g; 1.6 mmol), N,N-dimethylformamide (6 ml), triethylamine (4 ml), bis(triphenylphosphine) palladium(II) chloride (0.11 g; 0.16 mmol) and copper iodide (31 mg; 0.16 mmol). The mixture was degassed under argon. The orange solution was heated in the microwave at 120° C. during 25 min. The mixture obtained was poured in brine and extracted three times with dichloromethane. Organic were combined, dried over sodium sulfate and evaporated under reduced pressure to provide the crude which was subject to flash chromatography (eluant: c-hexane/ethyl acetate 8:2). 290 mg (75% of theory) of 3-(2,4,6-trichloro-phenyl)-prop-2-yn-1-ol was obtained as a yellow solid. The mixture was degassed under argon The mixture obtained extracted three times with dichloromethane dried over sodium sulfate evaporated under reduced pressure to provide the crude which

反応条件: temp:12.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of paratoluene sulfonic acid monohydrate (14.5 g; 76.4 mmol) in acetonitrile (100 ml) was added the 2,4,6-trichloroaniline (5.0 g; 25.5 mmol). The resulting white suspension was cooled to 10-15° C. and to this was added, gradually a solution of sodium nitrite (3.5 g; 51.0 mmol) and potassium iodide (10.6 g; 63.6 mmol) in water (15 ml), the suspension became dark brown, thick and gas release was observed. The thick mixture was stirred for 10 min at 10° C. and then temperature was allowed to increase to 20° C. The solution obtained was stirred for 1 h. The solution was poured in water, 1M sodium hydrogen carbonate solution was added (pH adjusted to 9-10) and 2M solution of sodium thiosulfate was added. The mixture was extracted three times with dichloromethane. Organics were combined, dried over sodium sulfate and the solvent was removed in vacuo to provide a resin which was subject to flash column chromatography (eluant: c-hexane). 6.3 g (80% of theory) of 1,3,5-trichloro-2-iodo-benzene was obtained as a white solid. to this was added to increase to 20° C The solution obtained was stirred for 1 h was added The mixture was extracted three times with dichloromethane dried over sodium sulfate the solvent was removed in vacuo to provide a resin which

反応条件: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Add 1-iodo-2,4,6-trichlorobenzene (1500 mg, 4.88 mmol), zinc cyanide (345 mg, 2.94 mmol) and tetrakis(triphenylphosphine)palladium(0) (282 mg, 0.244 mmol) to anhydrous DMF (30 mL). Heat to 85° C. overnight. Cool to room temperature, dilute with toluene, wash with 2 N ammonium hydroxide (3×) and saturated aqueous sodium chloride and concentrate. Purify by silica gel chromatography, eluting with hexanes/dichloromethane to give 2,4,6-trichlorobenzonitrile (850 mg, 84%): 1H NMR (400 MHz, CDCl3) δ 7.76 (s, 1H), 7.65 (s, 1H). Cool to room temperature wash with 2 N ammonium hydroxide (3×) and saturated aqueous sodium chloride concentrate Purify by silica gel chromatography eluting with hexanes/dichloromethane