1,4-dichloro-2-methoxybenzene

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 900 mL of ammonia was condensed at −78° C. 1 g of thinly shaven strips of sodium was added followed by 1.0 g of iron (III) nitrate nonahydrate. Upon disappearance of the deep blue color 25 g of thinly shaven strips of sodium was added. After 30 mins of stirring at −78° C., 50 g of 2,5-dichloroanisole was added as a solution in hexane (70 mL) dropwise and the reaction warmed to −45° C. for 2 hrs. Upon completion the ammonia was allowed to evaporate. The crude pot was then diluted in chloroform and 100 g of NH4Cl was added slowly. The combines were taken up in a separatory funnel and washed with water (3×) followed by brine (1×). The organic layer was dried over sodium sulfate and concentrated in vacuo. The resulting solid can be used without further purification. Yield: 99%. condensed at −78° C the reaction warmed to −45° C. for 2 hrs to evaporate The crude pot was then diluted in chloroform 100 g of NH4Cl was added slowly The combines were taken up in a separatory funnel washed with water (3×) The organic layer was dried over sodium sulfate concentrated in vacuo The resulting solid can be used without further purification

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

実験手順: Dimethylsulfate (94.64 g) is added dropwise over a 40 minute period to a cooled stirred solution of 2,5-dichlorophenol (122.25 g) and sodium hydroxide (31.5 g) in water (300 ml). This mixture is stirred at room temperature for one hour, then at reflux for 2 hours, then cooled to room temperature. The organic layer is separated and combined with ether extracts of the remaining aqueous layer. The ether solution is dried (saturated NaCl, Na2SO4, K2CO3) and the ether removed to give 2,5-dichloroanisole. Distillation gives a colorless liquid (115° C. at aspirator vacuum). at reflux for 2 hours cooled to room temperature The organic layer is separated The ether solution is dried (saturated NaCl, Na2SO4, K2CO3) the ether removed

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

実験手順: Dimethylsulfate (94.64 g) is added dropwise over a 40 minute period to a cooled stirred solution of 2,5-dichlorophenol (122.25 g) and sodium hydroxide (31.5 g) in water (300 ml). This mixture is stirred at room temperature for one hour, then at reflux for 2 hours, then cooled to room temperature. The organic layer is separated and combined with ether extracts of the remaining aqueous layer. The ether solution is dried (saturated NaCl, Na2SO4, K2CO3) and the ether removed to give 2,5-dichloroanisole. Distillation gives a colorless liquid (115° C. at aspirator vacuum). at reflux for 2 hours cooled to room temperature The organic layer is separated The ether solution is dried (saturated NaCl, Na2SO4, K2CO3) the ether removed

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

実験手順: Dimethylsulfate (94.64 g) is added dropwise over a 40 minute period to a cooled stirred solution of 2,5-dichlorophenol (122.25 g) and sodium hydroxide (31.5 g) in water (300 ml). This mixture is stirred at room temperature for one hour then at reflux for 2 hours, then cooled to room temperature. The organic layer is separated and combined with ether extracts of the remaining aqueous layer. The ether solution is dried (saturated NaCl, Na2SO4, K2CO3) and the ether removed to give 2,5-dichloroanisole. Distillation gives a colorless liquid (115° C. at aspirator vacuum). at reflux for 2 hours cooled to room temperature The organic layer is separated The ether solution is dried (saturated NaCl, Na2SO4, K2CO3) the ether removed

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 900 mL of ammonia was condensed at −78° C. 1 g of thinly shaven strips of sodium was added followed by 1.0 g of iron (III) nitrate nonahydrate. Upon disappearance of the deep blue color 25 g of thinly shaven strips of sodium was added. After 30 mins of stirring at −78° C., 50 g of 2,5-dichloroanisole was added as a solution in hexane (70 mL) dropwise and the reaction warmed to −45° C. for 2 hrs. Upon completion the ammonia was allowed to evaporate. The crude pot was then diluted in chloroform and 100 g of NH4Cl was added slowly. The combines were taken up in a separatory funnel and washed with water (3×) followed by brine (1×). The organic layer was dried over sodium sulfate and concentrated in vacuo. The resulting solid can be used without further purification. Yield: 99%. condensed at −78° C the reaction warmed to −45° C. for 2 hrs to evaporate The crude pot was then diluted in chloroform 100 g of NH4Cl was added slowly The combines were taken up in a separatory funnel washed with water (3×) The organic layer was dried over sodium sulfate concentrated in vacuo The resulting solid can be used without further purification

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 900 mL of ammonia was condensed at −78° C. 1 g of thinly shaven strips of sodium was added followed by 1.0 g of iron (III) nitrate nonahydrate. Upon disappearance of the deep blue color 25 g of thinly shaven strips of sodium was added. After 30 mins of stirring at −78° C., 50 g of 2,5-dichloroanisole was added as a solution in hexane (70 mL) dropwise and the reaction warmed to −45° C. for 2 hrs. Upon completion the ammonia was allowed to evaporate. The crude pot was then diluted in chloroform and 100 g of NH4Cl was added slowly. The combines were taken up in a separatory funnel and washed with water (3×) followed by brine (1×). The organic layer was dried over sodium sulfate and concentrated in vacuo. The resulting solid can be used without further purification. Yield: 99%. condensed at −78° C the reaction warmed to −45° C. for 2 hrs to evaporate The crude pot was then diluted in chloroform 100 g of NH4Cl was added slowly The combines were taken up in a separatory funnel washed with water (3×) The organic layer was dried over sodium sulfate concentrated in vacuo The resulting solid can be used without further purification

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: 4-Methoxy-2,2',4',5,5'-pentachlorobiphenyl was prepared from 2,5-Dichloroanisole (35 g, 200 mmol) and 2,4,5-trichloroaniline (2.95 g, 15 mmol) according to the procedure in Example 2A. The excess dichloroanisole was removed by distillation and the residue was then filtered through silica gel (heptane eluent) and further purified [Chromatotron®, 4 mm silica gel, hexane, 20 mL/min] to give the product (980 mg). Mass spectrum: m/z at 354 for C13H7Cl5O. The excess dichloroanisole was removed by distillation the residue was then filtered through silica gel (heptane eluent) further purified [Chromatotron®, 4 mm silica gel, hexane, 20 mL/min]

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

実験手順: To a suspension of 2,4,5-trichloroaniline (1.96 g, 10 mmol) in 30 mL 35% H2SO4 in an ice/salt bath (below 0° C.) was added a solution of sodium nitrite (0.828 mg, 12 mmol) in 50 ml cold distilled water. The yellow mixture was allowed to stir below 0° C. for 45 minutes at which time it was added to a vigorously stirred solution of 2,5-dichloroanisole (1.76 g, 10 mmol) in 100 mL CCl4 below 0° C. Saturated sodium acetate solution was added until a pH≥7 was obtained. The resulting mixture was allowed to warm to room temperature, then stirred 18 h. The reaction was extracted with several portions of CH2Cl2 and the combined organic layers were dried with anhydrous Na2SO4, filtered, then concentrated to a heavy oil. The oil was distilled (150°-200° C., 0.2 mm Hg) through a Kugelrhor apparatus to yield 0.8 g of a dark yellow oil. The distillate was further purified via flash chromatography (silica gel, hexane eluent). Fraction 1 (40 mg; Rf=0.38; GC retention time=16.32 minutes) was identified as 2,2',4',5,5'-pentachloro-6-methoxybiphenyl. Fraction 2 (262 mg, 7.4% yield; Rf=0.33) was found to contain 2,5,2',4',5'-pentachloro-3-methoxy and 2,5,2',4',5'-pentachloro-4-methoxybiphenyl in a 17:83 ratio as determined by GC (RT=17.58, 17.75 minutes respectively) and NMR analyses. cold distilled water was obtained stirred 18 h The reaction was extracted with several portions of CH2Cl2 the combined organic layers were dried with anhydrous Na2SO4 filtered concentrated to a heavy oil The oil was distilled (150°-200° C., 0.2 mm Hg) through a Kugelrhor apparatus

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

実験手順: Anhydrous K2CO3 (21.9 g, 0.159 mol) and methyl iodide (10.8 mL, 0.178 mol) were added to a solution of 2,5-dichlorophenol (23.5 g, 0.144 mol) in 215 mL acetone. The reaction was allowed to stir at room temperature for 20 hours, then filtered through a celite pad. The filtrate was concentrated to a residue which was taken up in diethylether. The ether solution was washed with 10% NaHSO3, water, several portions of 1M NaOH, and brine, then dried with anhydrous Na2SO4. Upon filtration and concentration, the residue was distilled (8 mm Hg, 110° C.) to yield 23.7 g (93.5%) of a light yellow oil. filtered through a celite pad The filtrate was concentrated to a residue which The ether solution was washed with 10% NaHSO3, water, several portions of 1M NaOH, and brine dried with anhydrous Na2SO4 Upon filtration and concentration the residue was distilled (8 mm Hg, 110° C.)

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

実験手順: To a suspension of 2,4,5-trichloroaniline (1.96 g, 10 mmol) in 30 mL 35% H2SO4 in an ice/salt bath (below 0° C.) was added a solution of sodium nitrite (0.828 mg, 12 mmol) in 50 ml cold distilled water. The yellow mixture was allowed to stir below 0° C. for 45 minutes at which time it was added to a vigorously stirred solution of 2,5-dichloroanisole (1.76 g, 10 mmol) in 100 mL CCl4 below 0° C. Saturated sodium acetate solution was added until a pH≧7 was obtained. The resulting mixture was allowed to warm to room temperature, then stirred 18 h. The reaction was extracted with several portions of CH2Cl2 and the combined organic layers were dried with anhydrous Na2SO4, filtered, then concentrated to a heavy oil. The oil was distilled (150-200° C., 0.2 mm Hg) through a Kugelrhor apparatus to yield 0.8 g of a dark yellow oil. The distillate was further purified via flash chromatography (silica gel, hexane eluent). Fraction 1 (40 mg; Rf=0.38; GC retention time=16.32 minutes) was identified as 2,2′,4′,5,5′-pentachloro-6-methoxybiphenyl. Fraction 2 (262 mg, 7.4% yield; Rf=0.33) was found to contain 2,5,2′,4′,5′-pentachloro-3-methoxy and 2,5,2′,4′,5′-pentachloro-4-methoxybiphenyl in a 17:83 ratio as determined by GC (RT=17.58, 17.75 minutes respectively) and NMR analyses. cold distilled water was obtained stirred 18 h The reaction was extracted with several portions of CH2Cl2 the combined organic layers were dried with anhydrous Na2SO4 filtered concentrated to a heavy oil The oil was distilled (150-200° C., 0.2 mm Hg) through a Kugelrhor apparatus