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