Ethyl Thioglycolate → HCID 10967505, compound

Temperature

0 °C

1,4-dimethoxy-2,3-dibromomethylbenzene (10.0 g, 30.88 mmol) was dissolved in CH2Cl2 and MeOH (750 ml, 6:4) followed by addition of ethyl 2-mercaptoacetate (4.02 ml, 37.06 mmol) with stirring under argon. The mixture was then cooled to 0° C. followed by dropwise addition of sodium methoxide (4.37M, 8.5 ml, 37.06 mmol) over a period of 2 h using an automatic syringe pump. After 5 minutes the solvent was evaporated and the crude was redissolved in THF (400 ml) and cooled to 0° C. again. NaOEt (2.10 g, 30.88 mmol) was then added. The ice bath was removed and the reaction was stirred for 2 more hours. The reaction mixture was then quenched with NH4Cl (sat.) and extracted with ether. The organic phases were combined, dried over MgSO4, filtered and concentrated. The crude residue was then treated with NaOME in MeOH and THF at 0° C. for 2 hours. The reaction mixture was extracted with ether (100 ml×2). The combined organic phases were washed with H2O, dried over MgSO4, filtered and concentrated to a residue that was purified by flash chromatography to give title compound in 45% yield. 1H NMR (300 MHz, CDCl3, ppm) d:2.97 (dd, 1H, J=16.51, 8.79 Hz, HCHaCHC=O), 3.36 (dd, 1H, J=16.7, 5.1 Hz, HCHeCHC=O), 3.73 (m, 2H, HCHa,e--O), 3.75 (s, 3H, OCH3), 3.78 (s, 6H, 2×OCH3), 3.85 (m, 1H, HC--S), 6.69 (m, 2H, ArH).

1. customAfter 5 minutes the solvent was evaporated
2. dissolutionthe crude was redissolved in THF (400 ml)
3. temperaturecooled to 0° C. again
4. customThe ice bath was removed
5. stirringthe reaction was stirred for 2 more hours
6. customThe reaction mixture was then quenched with NH4Cl (sat.)
7. extractionextracted with ether
8. dry with materialdried over MgSO4
9. filtrationfiltered
10. concentrationconcentrated
11. additionThe crude residue was then treated with NaOME in MeOH
12. extractionThe reaction mixture was extracted with ether (100 ml×2)
13. washThe combined organic phases were washed with H2O
14. dry with materialdried over MgSO4
15. filtrationfiltered
16. concentrationconcentrated to a residue that
17. customwas purified by flash chromatography

ORD record

ord-841c131c32a74df8ae9336225ef2442a

Source dataset

uspto-grants-1997_01

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05593970