反应详情

温度

100 °C

A 20-L stainless steel vessel equipped with a mechanical stirrer and a dropping funnel was charged with a solution of 4-chloro-5-cyclopentyloxy-2-fluorophenylisocyanate (4.00 kg, 15.6 mol) and methyl 2-hydroxy-3-methyl-3-butenoate (2.40 kg; purity=ca. 90%; 18.4 mol) in toluene (10 L). To the solution being cooled in an ice water bath, triethylamine (40 mL) was added dropwise slowly enough to ensure against the increase in the temperature of the solution. The solution was stirred at the same temperature for 3 h until TLC confirmed that the starting materials had disappeared. Subsequently, potassium carbonate (200 g) was added and, with the resulting methanol being removed with a fitted distillator, the mixture was stirred under heating in a water bath (100° C.) for 5 h. After completion of the reaction, the reaction mixture was washed with 1N HCl (10 L), 1N sodium hydroxide (10 L) and again with 1N HCl (10 L). The toluene layer was dried with anhydrous magnesium sulfate and the solvent was distilled off under vacuum; thereafter, hexane was added in an amount about one half of the resulting oil and the mixture was left to stand at room temperature, thereby producing 3N-(4-chloro-5-cyclopentyloxy-2-fluorophenyl)-5-isopropyliden-2,4-oxazolidinedione as whitish yellow solids (4.19 kg, 11.8 mol; yield=75.7%; primary crystal). MP: 104.5°-105.0° C. 1H-NMR(CDCl3,TMS,ppm): δ1.49-1.97(8H,m), 2.03(3H,s), 2.31(3H,s), 4.73(1H,m), 6.88(1H,d,JHF =6.6Hz), 7.33(1H,d,JHF =8.5Hz). IR (KBr disk, cm-1): 2970, 1815, 1740, 1500, 1200.

1. temperatureTo the solution being cooled in an ice water bath
2. temperatureincrease in the temperature of the solution
3. customremoved with a fitted distillator
4. stirringthe mixture was stirred
5. customAfter completion of the reaction
6. washthe reaction mixture was washed with 1N HCl (10 L), 1N sodium hydroxide (10 L) and again with 1N HCl (10 L)
7. dry with materialThe toluene layer was dried with anhydrous magnesium sulfate
8. distillationthe solvent was distilled off under vacuum
9. additionthereafter, hexane was added in an amount about one half of the resulting oil
10. waitthe mixture was left
11. customto stand at room temperature