1,2,3,4,5,6-hexachlorobenzene

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:-40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Hexachlorobenzene (35 g) was slurried in 160 ml of anhydrous ethyl ether at −40° C. A 2.5 M hexanes solution of n-butyllithium (54.1 mL) was added, and the reaction was stirred for 30 minutes at −40° C. Perfluoro-2-ethoxyacetylfluoride (40 g, 72% pure, prepared from 2-ethoxyethyl acetate by the method described in Example 1 of U.S. Pat. No. 5,326,919, incorporated herein by reference) was added to the −40° C. reaction mixture which was then allowed to warm slowly to room temperature. The reaction mixture was quenched with 200 mL of cold 5% aqueous HCl. The aqueous mixture was extracted with ethyl ether and the extracts were dried over MgSO4 and rotary evaporated to give pentachlorophenyl perfluoroethoxymethyl ketone (49% crude yield). Vacuum distillation (105-109° C., 240 Pa) using a 15 cm Vigreux column gave 19.7 g of a colorless liquid which slowly crystallized on standing. 5,326,919, incorporated herein by reference) was added to the −40° C. reaction mixture which to warm slowly to room temperature The reaction mixture was quenched with 200 mL of cold 5% aqueous HCl The aqueous mixture was extracted with ethyl ether the extracts were dried over MgSO4 rotary evaporated

反応条件: temp:-40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Hexachlorobenzene (35 g) was slurried in 160 ml of anhydrous ethyl ether at −40° C. A 2.5 M hexanes solution of n-butyllithium (54.1 mL) was added, and the reaction was stirred for 30 minutes at −40° C. Perfluoro-2-ethoxyacetylfluoride (40 g, 72% pure, prepared from 2-ethoxyethyl acetate by the method described in Example 1 of U.S. Pat. No. 5,326,919, incorporated herein by reference) was added to the −40° C. reaction mixture which was then allowed to warm slowly to room temperature. The reaction mixture was quenched with 200 mL of cold 5% aqueous HCl. The aqueous mixture was extracted with ethyl ether and the extracts were dried over MgSO4 and rotary evaporated to give pentachlorophenyl perfluoroethoxymethyl ketone (49% crude yield). Vacuum distillation (105-109° C., 240 Pa) using a 15 cm Vigreux column gave 19.7 g of a colorless liquid which slowly crystallized on standing. 5,326,919, incorporated herein by reference) was added to the −40° C. reaction mixture which to warm slowly to room temperature The reaction mixture was quenched with 200 mL of cold 5% aqueous HCl The aqueous mixture was extracted with ethyl ether the extracts were dried over MgSO4 rotary evaporated

反応条件: temp:-40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Hexachlorobenzene (35 g) was slurried in 160 ml of anhydrous ethyl ether at -40° C. A 2.5 M hexanes solution of n-butyllithium (54.1 mL) was added, and the reaction was stirred for 30 minutes at -40° C. Perfluoro-2-ethoxyacetylfluoride (40 g, 72% pure, prepared from 2-ethoxyethyl acetate by the method described in Example I of U.S. Pat. No. 5,326,919, incorporated herein by reference) was added to the -40° C. reaction mixture which was then allowed to warm slowly to room temperature. The reaction mixture was quenched with 200 mL of cold 5% aqueous HCl. The aqueous mixture was extracted with ethyl ether and the extracts were dried over MgSO4 and rotary evaporated to give pentachlorophenyl perfluoroethoxymethyl ketone (49% crude yield). Vacuum distillation (105-109° C., 240 Pa) using a 15 cm Vigreux column gave 19.7 g of a colorless liquid which slowly crystallized on standing. 5,326,919, incorporated herein by reference) was added to the -40° C. reaction mixture which to warm slowly to room temperature The reaction mixture was quenched with 200 mL of cold 5% aqueous HCl The aqueous mixture was extracted with ethyl ether the extracts were dried over MgSO4 rotary evaporated

反応条件: temp:-40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Hexachlorobenzene (35 g) was slurried in 160 ml of anhydrous ethyl ether at −40° C. A 2.5 M hexanes solution of n-butyllithium (54.1 mL) was added, and the reaction was stirred for 30 minutes at −40° C. Perfluoro-2-ethoxyacetylfluoride (40 g, 72 % pure, prepared from 2-ethoxyethyl acetate by the method described in Example 1 of U.S. Pat. No. 5,326,919, incorporated herein by reference) was added to the −40° C. reaction mixture which was then allowed to warm slowly to room temperature. The reaction mixture was quenched with 200 mL of cold 5% aqueous HCl. The aqueous mixture was extracted with ethyl ether and the extracts were dried over MgSO4 and rotary evaporated to give pentachlorophenyl perfluoroethoxymethyl ketone (49% crude yield). Vacuum distillation (105-109° C., 240 Pa) using a 15 cm Vigreux column gave 19.7 g of a colorless liquid which slowly crystallized on standing. 5,326,919, incorporated herein by reference) was added to the −40° C. reaction mixture which to warm slowly to room temperature The reaction mixture was quenched with 200 mL of cold 5% aqueous HCl The aqueous mixture was extracted with ethyl ether the extracts were dried over MgSO4 rotary evaporated

反応条件: temp:-40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Hexachlorobenzene (35 g) was slurried in 160 ml of anhydrous ethyl ether at −40° C. A 2.5 M hexanes solution of n-butyllithium (54.1 mL) was added, and the reaction was stirred for 30 minutes at −40° C. Perfluoro-2-ethoxyacetylfluoride (40 g, 72% pure, prepared from 2-ethoxyethyl acetate by the method described in Example 1 of U.S. Pat. No. 5,326,919, incorporated herein by reference) was added to the −40° C. reaction mixture which was then allowed to warm slowly to room temperature. The reaction mixture was quenched with 200 mL of cold 5% aqueous HCl. The aqueous mixture was extracted with ethyl ether and the extracts were dried over MgSO4 and rotary evaporated to give pentachlorophenyl perfluoroethoxymethyl ketone (49% crude yield). Vacuum distillation (105-109° C., 240 Pa) using a 15 cm Vigreux column gave 19.7 g of a colorless liquid which slowly crystallized on standing. 5,326,919, incorporated herein by reference) was added to the −40° C. reaction mixture which to warm slowly to room temperature The reaction mixture was quenched with 200 mL of cold 5% aqueous HCl The aqueous mixture was extracted with ethyl ether the extracts were dried over MgSO4 rotary evaporated

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:-40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Hexachlorobenzene (35 g) was slurried in 160 ml of anhydrous ethyl ether at −40° C. A 2.5 M hexanes solution of n-butyllithium (54.1 mL) was added, and the reaction was stirred for 30 minutes at −40° C. Perfluoro-2-ethoxyacetylfluoride (40 g, 72% pure, prepared from 2-ethoxyethyl acetate by the method described in Example 1 of U.S. Pat. No. 5,326,919, incorporated herein by reference) was added to the −40° C. reaction mixture which was then allowed to warm slowly to room temperature. The reaction mixture was quenched with 200 mL of cold 5% aqueous HCl. The aqueous mixture was extracted with ethyl ether and the extracts were dried over MgSO4 and rotary evaporated to give pentachlorophenyl perfluoroethoxymethyl ketone (49% crude yield). Vacuum distillation (105-109° C., 240 Pa) using a 15 cm Vigreux column gave 19.7 g of a colorless liquid which slowly crystallized on standing. 5,326,919, incorporated herein by reference) was added to the −40° C. reaction mixture which to warm slowly to room temperature The reaction mixture was quenched with 200 mL of cold 5% aqueous HCl The aqueous mixture was extracted with ethyl ether the extracts were dried over MgSO4 rotary evaporated

反応条件: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Pentachlorothiophenol (10.0 g, 0.035 mol) was added to 60.0 g of 99% nitric acid over 20 min at 45°-50° C. followed by heating at reflux (55° C.) for 1.5 hr. At this point 20 mL of 30% by weight oleum was added at such a rate that the temperature was kept at 75° to 80° C. After the addition was complete (approximately 30 min.), the reaction mixture was cooled to room temperature. The product was collected by filtration, and thoroughly washed with water to give after drying in vacuo, 8.6 g (85% yield) of 99.7% PCNB with 0.17% hexachlorobenzene (GC assay). Variations on this one-pot, two-step process were examined and are summarized in TABLE I. by heating was kept at 75° to 80° C After the addition (approximately 30 min.) the reaction mixture was cooled to room temperature The product was collected by filtration thoroughly washed with water to give

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

実験手順: Pentachlorothiophenol (10.0 g, 0.035 mol) was added to 60.0 g of 70% nitric acid at room temperature. The reaction mixture was heated at reflux 7 hr followed by stirring at room temperature 16 hr. At this point, 40 mL of 30% oleum (30% by weight sulfur trioxide in sulfuric acid) was added at such a rate that the temperature was maintained between 55° and 60° C. After the addition was complete (30 min), the reaction mixture was heated at 108° C. for 30 minutes. The reaction mixture was then cooled to room temperature, filtered, the product washed with water and dried in vacuo to give 7.6 g (74% yield) of 99.0% PCNB with 1.0% hexachlorobenzene (GC assay). The reaction mixture was heated at reflux 7 hr was maintained between 55° and 60° C After the addition (30 min) the reaction mixture was heated at 108° C. for 30 minutes The reaction mixture was then cooled to room temperature filtered the product washed with water dried in vacuo

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

実験手順: Hexachlorobenzene (25.0 g, 0.088 mol) was added to 50 mL of dimethylformamide followed by the addition of 7.4 g (0.096 mol) of 73% sodium hydrosulfide and 7.9 mL (0.079 mol) of 40% aqueous sodium hydroxide. The stirred reaction mixture was heated to 85° C. for 3.0 hr, cooled to room temperature, and poured into 200 mL of water. After 10 min of stirring, the insoluble material was removed by filtration, and the filtrate acidified with 15 mL (0.18 mol) of concentrated aqueous hydrochloric acid. The resulting precipitate was collected by filtration, washed with 100 mL of water, and dried in vacuo giving 22.8 g, 92% of theoretical, of pentachlorothiophenol. The stirred reaction mixture cooled to room temperature the insoluble material was removed by filtration The resulting precipitate was collected by filtration washed with 100 mL of water dried in vacuo

反応条件: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Pentachlorothiophenol (10.0 g, 0.035 mol) was added to 60.0 g of 99% nitric acid over 20 min at 45°-50° C. followed by heating at reflux (55° C.) for 1.5 hr. At this point 20 mL of 30% by weight oleum was added at such a rate that the temperature was kept at 75° to 80° C. After the addition was complete (approximately 30 min.), the reaction mixture was cooled to room temperature. The product was collected by filtration, and thoroughly washed with water to give after drying in vacuo, 8.6 g (85% yield) of 99.7% PCNB with 0.17% hexachlorobenzene (GC assay). Variations on this one-pot, two-step process were examined and are summarized in TABLE I. by heating was kept at 75° to 80° C After the addition (approximately 30 min.) the reaction mixture was cooled to room temperature The product was collected by filtration thoroughly washed with water to give