1-dichlorophosphoryloxyethane

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

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: Pyrocatechol (1.249 g, 11.35 mM) was dissolved in 42 ml of ether and, using 2.297 g (22.70 mM) of triethylamine and 1.849 g (11.35 mM) of ethyl dichlorophosphate, the reaction was carried out at -40° C. to -35° C. and the reaction mixture treated in the same manner as in Reference Example 1. There was obtained 2.159 g (95.0% yield) of ethyl o-phenylene phosphate as a colorless viscous oil. was carried out at -40° C. to -35° C. the reaction mixture treated in the same manner as in Reference Example 1

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

実験手順: Under an argon stream, 10 g of 1,4-bis(hydroxyethyl) terephthalate (BHET), 9.61 g of 4-dimethylaminopyridine (DMAP), and 70 mL of methylene chloride were placed in a 250 mL flask equipped with a funnel. The solution in the flask was cooled down to −40° C. with stirring, and a solution of 5.13 g of ethyl phosphorodichloridate (EOP) (distilled before use) in 20 mL of methylene chloride was added dropwise through the funnel. After addition was complete, the mixture was stirred at room temperature for four hours to form the homopolymer BHET-EOP. equipped with a funnel After addition the mixture was stirred at room temperature for four hours

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

実験手順: 4-Hydroxy-3-(2-hydroxy-1,1-dimethylethyl)phenyl methanesulphonate (10g) from Example 1 was suspended in acetonitrile (100 ml) and triethylamine (8g) was added. The mixture was cooled in ice, and ethyl phosphorodichloridate (6.9g) was added dropwise with vigorous stirring. Stirring was continued for 6 hours prior to the addition of dichloromethane (200 ml), after which the solution was washed with water, dilute sodium hydroxide solution and water again, dried over magnesium sulphate and run down. The crude product was recrystallised from toluene, yielding 6.0g of the desired product, melting point 113°-115° C. The mixture was cooled in ice after which the solution was washed with water, dilute sodium hydroxide solution and water again dried over magnesium sulphate The crude product was recrystallised from toluene

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of N-acetyl-colchicinol (1) (0.36 g; 1.0 mmol) in THF (40 ml) under argon was cooled to 0° C. and treated with a 1.0M solution of lithiumHMDS in THF (1.1 ml; 1.1 mmol). The mixture was stirred at 0° C. for 1 hour and then added in portions over about 2 hours to a solution of ethyl dichlorophosphate (400 μl; 3.3 mmol) in THF (150 ml). The mixture was stirred at ambient temperature for 15 minutes. After addition of water (200 ml) the THF was removed by evaporation. After removal of the insoluble material by filtration, the filtrate was purified on HP20 SS resin eluting with a gradient of 0–60% methanol/water. The appropriate fractions were freeze-dried to give (5S)-5-(acetylamino)-9,10,11-trimethoxy-6,7-dihydro-5H-dibenzo[a,c]cyclohepten-3-yl ethyl hydrogen phosphate as a white solid (259 mg). The mixture was stirred at ambient temperature for 15 minutes was removed by evaporation After removal of the insoluble material by filtration the filtrate was purified on HP20 SS resin eluting with a gradient of 0–60% methanol/water The appropriate fractions were freeze-dried

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

実験手順: Under an argon stream, 10 g of 1,4-bis(hydroxyethyl)terephthalate (BHET), 9.61 g of 4-dimethylaminopyridine (DMAP), and 70 mL of methylene chloride were placed in a 250 mL flask equipped with a funnel. The solution in the flask was cooled down to −40° C. with stirring, and a solution of 5.13 g of ethyl phosphorodichloridate (EOP) (distilled before use) in 20 mL of methylene chloride was added dropwise through the funnel. After addition was complete, the mixture was stirred at room temperature for four hours to form the homopolymer BHET-EOP. equipped with a funnel After addition the mixture was stirred at room temperature for four hours

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

実験手順: Under an argon stream, 10 g of 1,4-bis(hydroxyethyl) terephthalate (BHET) prepared as described above in Example 1, 9.61 g of 4-dimethylaminopyridine (DMAP), and 70 mL of methylene chloride were placed in a 250 mL flask equipped with a funnel. The solution in the flask was cooled down to −40° C. with stirring, and a solution of 5.13 g of ethyl phosphorodichloridate (EOP) (distilled before use) in 20 mL of methylene chloride was added dropwise through the funnel. After addition was complete, the mixture was stirred at room temperature for four hours to form the homopolymer BHET-EOP. were placed in a 250 mL flask equipped with a funnel After addition the mixture was stirred at room temperature for four hours

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

実験手順: Under an argon stream, 10 g of 1,4-bis(hydroxyethyl) terephthalate (BHET) prepared as described above in Example 1, 9.61 g of 4-dimethylaminopyridine (DMAP), and 70 mL of methylene chloride were placed in a 250 mL flask equipped with a funnel. The solution in the flask was cooled down to −40° C. with stirring, and a solution of 5.13 g of ethyl phosphorodichloridate (EOP) (distilled before use) in 20 mL of methylene chloride was added dropwise through the funnel. After addition was complete, the mixture was stirred at room temperature for four hours to form the homopolymer BHET-EOP. were placed in a 250 mL flask equipped with a funnel After addition the mixture was stirred at room temperature for four hours

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

実験手順: Pyrocatechol (1.249 g, 11.35 mM) was dissolved in 42 ml of ether and, using 2.297 g (22.70 mM) of triethylamine and 1.849 g (11.35 mM) of ethyl dichlorophosphate, the reaction was carried out at -40° C. to -35° C. and the reaction mixture treated in the same manner as in Reference Example 1. There was obtained 2.159 g (95.0% yield) of ethyl o-phenylene phosphate as a colorless viscous oil. was carried out at -40° C. to -35° C. the reaction mixture treated in the same manner as in Reference Example 1

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

実験手順: 4-Hydroxy-3-(2-hydroxy-1,1-dimethylethyl)phenyl methanesulphonate (10 g) from Example 1 was suspended in acetonitrile (100 ml) and triethylamine (8 g) was added. The mixture was cooled in ice, and ethyl phosphorodichloridate (6.9 g) was added dropwise with vigorous stirring. Stirring was continued for 6 hours prior to the addition of dichloromethane (200 ml), after which the solution was washed with water, dilute sodium hydroxide solution and water again, dried over magnesium sulphate and run down. The crude product was recrystallised from toluene, yielding 6.0 g of the desired product, melting point 113°-115° C. The mixture was cooled in ice after which the solution was washed with water, dilute sodium hydroxide solution and water again dried over magnesium sulphate The crude product was recrystallised from toluene