Hydrochloric Acid → HCID 53682263, compound

Temperature

-5 °C

Sodium hydride (17.32 g, 0.433 mol) was washed with hexane (100 ml×2) then was suspended in dimethylformamide (300 ml). To the mixture was dropwise added thiophenol (44.5 ml, 0.433 mol) in DMF (50 ml) under ice-methanol bath cooling with controlling the inner temperature of 5-10° C. under nitrogen atmosphere. After 1.5 h stirring at -5° C., methyl 4-chloroacetoacetate (50 ml, 0.433 mol) was dropwise added to the reaction mixture under ice-methanol bath cooling with controlling the inner temperature of 5-10° C. under nitrogen atmosphere and the reaction mixture was stirred at room temperature overnight. The mixture was acidified with 1N HCl to pH 2 under ice bath cooling then partitioned between EtOAc (500 ml) and H2O (100 ml). The aqueous phase was extracted with EtOAc (250 ml×2). The combined extracts were concentrated to about 500 ml and then washed with aq. NaHCO3 solution (150 ml) and brine (100 ml×3). The organic solution was dried over MgSO4 and concentrated to afford 100.88 g of methyl 4-phenylthioacetoacetate as an orange color oil. (104% yield).(contained 1/6 eq of DMF) 1H NMR (CDCl3) 7.42-7.18 (m, 5H), 3.80 (s 2H), 3.71 (s, 3H), 3.65 (s, 2H).

1. temperaturecooling
2. customthe inner temperature of 5-10° C.
3. temperaturecooling
4. customthe inner temperature of 5-10° C.
5. stirringthe reaction mixture was stirred at room temperature overnight
6. temperaturecooling
7. customthen partitioned between EtOAc (500 ml) and H2O (100 ml)
8. extractionThe aqueous phase was extracted with EtOAc (250 ml×2)
9. concentrationThe combined extracts were concentrated to about 500 ml
10. washwashed with aq. NaHCO3 solution (150 ml) and brine (100 ml×3)
11. dry with materialThe organic solution was dried over MgSO4
12. concentrationconcentrated

ORD record

ord-847b77040ce445898e0e895d2c544527

Source dataset

uspto-grants-2000_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06131226