Background and overview[1]
Dimethyl phosphate is a colorless oily liquid with a boiling point of 78~80°C (0.glycerol 133 Pa). Soluble in water, alkaline solution, ethanol, chloroform, insoluble in benzene, ether and petroleum ether. It can be used as pesticide and pharmaceutical intermediates. P-(diazomethyl)dimethylphosphate is a derivative of dimethylphosphate and can be used as a pharmaceutical synthesis intermediate. If P-(diazomethyl)dimethylphosphate is inhaled, please move the patient to fresh air; if skin contact occurs, take off contaminated clothing, rinse the skin thoroughly with soap and water, and seek medical attention if you feel unwell. ; If eye contact occurs, separate eyelids, rinse with running water or saline, and seek medical attention immediately; if ingested, rinse mouth immediately, do not induce vomiting, and seek medical attention immediately.
Preparation method[1]
P-(diazomethyl)dimethylphosphate is prepared using fumed silica:
The specific steps are as follows: To a suspension of NaN3 (1.17g, 18.1mmol, 1.5 equivalent) in 23mL MeCN, add methanesulfonyl chloride (1.40mL, 2.07 g, 18.1mmol, 1.50 equivalent). The suspension was stirred at room temperature for 1 hour, then dimethyl (2-oxopropyl)phosphonate (1.66 mL, 2.00 g, 12.0 mmol, 1.00 equiv) was added dropwise. The reaction mixture was stirred at room temperature for 5 hours. Then, Cs2CO3 (5.88 g, 18.1 mmol, 1.50 equiv) was added, and the yellow suspension was stirred at room temperature for a further 14 hours. After adding 23 mL of MeOH, the reaction was stirred for 1 hour and then quenched by the addition of 20 mL of NH4Cl solution. The layers were separated and the aqueous layer was extracted with EtOAc (4 x 20 mL). The combined organic layers were washed with brine (1 × 100 mL), dried over Na2SO4, and volatiles were removed in vacuo. The crude product was purified by flash chromatography (425 cm, Et2O) to give the title compound P-(diazomethyl)dimethylphosphate as a yellow oil (1.10 g, 7.32 mmol, 59 %).
Main reference materials
[1] Synthesis of Chiral Thiourea-Thioxanthone Hybrids
