1-[ethoxy(ethyl)phosphoryl]oxyethane

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: 172 g of diethyl fumarate are slowly added at 65°-70° C. under nitrogen to a mixture of 140 g of diethyl ethanephosphonate in 46 g of ethanol. After a further 3 hours the solvent (excess ethanol and diethyl ether) is removed by vacuum distillation; the crude product is obtained in a yield of 285 g with a 95.7% purity, which corresponds to a theoretical yield of 90.9%. After a further 3 hours the solvent (excess ethanol and diethyl ether) is removed by vacuum distillation

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

実験手順: 172 g of diethyl fumarate are slowly added at 65°-70° C. under nitrogen to a mixture of 140 g of diethyl ethanephosphonate in 46 g of ethanol. After a further 3 hours the solvent (excess ethanol and diethyl ether) is removed by vacuum distillation; the crude product is obtained in a yield of 285 g with a 95.7% purity, which corresponds to a theoretical yield of 90.9%. After a further 3 hours the solvent (excess ethanol and diethyl ether) is removed by vacuum distillation

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

実験手順: Using the method described in Example 1, 12.76 g (0.05 mol) of pentachloropyridine is reacted with 4.1 g (0.063 gram atom) of zinc dust and 7.22 g (0.135 mol) of ammonium chloride, the solvent being in this case diethylethanephosphonate instead of dimethylmethanephosphonate. There is obtained 10.2 g (93% of theory) of crude 2,3,5,6-tetrachloropyridine, m.p. 86° to 88° C., which contains, according to gas-chromatographical analysis, 92.7% of 2,3,5,6-tetrachloropyridine, 1.2% of 2,3,5-trichloropyridine, 2.2% of 2,3,6-trichloropyridine and 2.8% of pentachloropyridine.

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

実験手順: Using the method described in Example 1, 12.76 g (0.05 mol) of pentachloropyridine is reacted with 4.1 g (0.063 gram atom) of zinc dust and 7.22 g (0.135 mol) of ammonium chloride, the solvent being in this case diethylethanephosphonate instead of dimethylmethanephosphonate. There is obtained 10.2 g (93% of theory) of crude 2,3,5,6-tetrachloropyridine, m.p. 86° to 88° C., which contains, according to gas-chromatographical analysis, 92.7% of 2,3,5,6-tetrachloropyridine, 1.2% of 2,3,5-trichloropyridine, 2.2% of 2,3,6-trichloropyridine and 2.8% of pentachloropyridine.

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

実験手順: Aluminum ethyl ethylphosphonate was prepared according to a known procedure: Diethyl ethylphosphonate (414 g), sodium hydroxide (199.5), and water (2.4 L) were refluxed for 4 h. A solution of aluminum sulfate hydrate (261 g) in water (830 mL) was then slowly added to form a white slurry. After filtration and drying, 319.7 g of aluminum ethyl ethylphosphonate was obtained as a white solid. Aluminum ethyl ethylphosphonate was prepared to form a white slurry After filtration drying

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

実験手順: Aluminum ethyl ethylphosphonate was prepared according to a known procedure: Diethyl ethylphosphonate (414 g), sodium hydroxide (199.5), and water (2.4 L) were refluxed for 4 h. A solution of aluminum sulfate hydrate (261 g) in water (830 mL) was then slowly added to form a white slurry. After filtration and drying, 319.7 g of aluminum ethyl ethylphosphonate was obtained as a white solid. Aluminum ethyl ethylphosphonate was prepared to form a white slurry After filtration drying

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

実験手順: Aluminum ethyl ethylphosphonate was prepared according to a known procedure: Diethyl ethylphosphonate (414 g), sodium hydroxide (199.5), and water (2.4 L) were refluxed for 4 h. A solution of aluminum sulfate hydrate (261 g) in water (830 mL) was then slowly added to form a white slurry. After filtration and drying, 319.7 g of aluminum ethyl ethylphosphonate was obtained as a white solid. Aluminum ethyl ethylphosphonate was prepared to form a white slurry After filtration drying

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

実験手順: Diethylethanephosphonate (68.2 g, 99%, 0.406 mole) was dripped into a 300 ml flask containing 33.3 g (99%, 0.402 mole) N-methylimidazole at 160° C. under nitrogen and stirring over a period of 80 minutes. The liquid was stirred at the same temperature for an additional 10 hours. The liquid was cooled, moved to a rotary evaporator and dried at 140° C./5 mmHg for 2.5 hours. The product (92.4 g, yield 92%) was a liquid at room temperature. 1H-NMR (CDCl3, 300.13 MHz, δ): 10.99 (s, 1H, —N—CH═N—), 7.73 (s, 1H, —N—CH═CH—N—), 7.65 (s, 1H, —N—CH═CH—N—), 4.39 (q, 2H, —N—CH2—CH3), 4.09 (s, 3H, —NCH3), 3.92 (m, 2H, —O—CH2—CH3), 1.56 (m, 3H, —OCH2—CH3), 1.56 (m, 2H, —(O═)P—CH2—CH3), 1.19 (m, 3H, —(O═)PCH2—CH3), 1.19 (m, 3H, —NCH2—CH3). 31P-NMR (CDCl3, 81.015 MHz, δ): 25.57 [s, RO—(R)P(═O)—O−]. The liquid was stirred at the same temperature for an additional 10 hours The liquid was cooled moved to a rotary evaporator dried at 140° C./5 mmHg for 2.5 hours

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

実験手順: 172 g of diethyl fumarate are slowly added at 65°-70° C. under nitrogen to a mixture of 140 g of diethyl ethanephosphonate in 46 g of ethanol. After a further 3 hours the solvent (excess ethanol and diethyl ether) is removed by vacuum distillation; the crude product is obtained in a yield of 285 g with a 95.7% purity, which corresponds to a theoretical yield of 90.9%. After a further 3 hours the solvent (excess ethanol and diethyl ether) is removed by vacuum distillation

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

実験手順: Using the method described in Example 1, 12.76 g (0.05 mol) of pentachloropyridine is reacted with 4.1 g (0.063 gram atom) of zinc dust and 7.22 g (0.135 mol) of ammonium chloride, the solvent being in this case diethylethanephosphonate instead of dimethylmethanephosphonate. There is obtained 10.2 g (93% of theory) of crude 2,3,5,6-tetrachloropyridine, m.p. 86° to 88° C., which contains, according to gas-chromatographical analysis, 92.7% of 2,3,5,6-tetrachloropyridine, 1.2% of 2,3,5-trichloropyridine, 2.2% of 2,3,6-trichloropyridine and 2.8% of pentachloropyridine.