O,O-DIETHYL THIOPHOSPHATE, POTASSIUM SALT

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Compound Spinosyn H (261 mg, 0.364 mmol) was dissolved in dry pyridine (3 ml). DMAP (60 mg) was added, followed by diethyl chlorothiophosphate (152 mg, 125 μl, 0.80 mmol). The reaction mixture was stirred at RT under nitrogen. After 12 hrs. toluene (50 ml) and EtOAc (50 ml) were added. The solution was extracted with brine, then with 5% aq. NaHCO3. The organic layer was dried over and Na2SO4 and concentrated in vacuo. The residue was purified over a flash SiO2 column (30 g/EtOAc) to give compound 2'R)-(diethyl)thiophosphate of Spinosyn H; 84 mg, 27%) CI MS m/z 870 (M+1); 1H-NMR (CDCl3) δ 6.74 (1H, bs), 4.80 (1H, m), 4.22 (4H, 2× CH2, m), 1.30 (6H, 2× CH3, m). The solution was extracted with brine The organic layer was dried over and Na2SO4 concentrated in vacuo The residue was purified over a flash SiO2 column (30 g/EtOAc)

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 4-[2-cyano-2-(4-trifluoromethoxyphenyl)ethyl]benzoic acid methyl ester (8.76 g, 25.08 mmol), water (4.7 mL) and diethyl thiophosphate (4.67 mL, 27.8 mmol) was stirred and heated to 80° C. for two hours. The mixture was cooled and aqueous sodium hydrogen carbonate (100 mL, 10%) and ethyl acetate (200 mL) were added. The organic phase was washed with brine. Drying (MgSO4) and concentration in vacuo afforded 7 g of the crude material, which was purified by column chromatography on silica gel eluting with a mixture of ethyl acetate:heptane 1:2, containing 2% ethanol. This afforded 2.6 g (27%.) of 4-[2-thiocarbamoyl-2-(4-trifluoromethoxy-phenyl)ethyl]benzoic acid methyl ester as a solid. The mixture was cooled The organic phase was washed with brine Drying (MgSO4) and concentration in vacuo

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Compound Spinosyn H (261 mg, 0.364 mmol) was dissolved in dry pyridine (3 ml). DMAP (60 mg) was added, followed by diethyl chlorothiophosphate (152 mg, 125 μl, 0.80 mmol). The reaction mixture was stirred at RT under nitrogen. After 12 hrs. toluene (50 ml) and EtOAc (50 ml) were added. The solution was extracted with brine, then with 5% aq. NaHCO3. The organic layer was dried over and Na2SO4 and concentrated in vacuo. The residue was purified over a flash SiO2 column (30 g/EtOAc) to give compound 2'R)-(diethyl)thiophosphate of Spinosyn H; 84 mg, 27%) CI MS m/z 870 (M+1); 1H-NMR (CDCl3) δ 6.74 (1H, bs), 4.80 (1H, m), 4.22 (4H, 2× CH2, m), 1.30 (6H, 2× CH3, m). The solution was extracted with brine The organic layer was dried over and Na2SO4 concentrated in vacuo The residue was purified over a flash SiO2 column (30 g/EtOAc)