(2,2-Dimethoxyethyl)(4-fluorophenyl)sulfane → 5-Fluoro-1-benzothiophene

Anhydrous chlorobenzene (1500 ml) was placed in a 3 liter 3-necked flask equipped with a condenser and a mechanical stirrer. The apparatus was flushed with nitrogen and about 495 grams of polyphosphoric acid (PPA) was added. The mixture was brought to gentle reflux and 161 g (0.74 mol) of crude (4-fluorophenylthio)- acetaldehyde dimethyl acetal was added during 2.5 hours and the solution was further refluxed for 19 hours. The reaction mixture was allowed to cool to ambient temperature and the organic phase was separated from the PPA. Residual PPA was decomposed with water and the resulting aqueous phase was extracted with toluene (2×150 ml). The combined organic phases was dried over MgSO4 and the solvents evaporated. The residue was fractionated to give 62.4 g (55%) of 5-fluorobenzothiophene which had b.p. 76°-77° C./ 4.5 mm Hg and m.p. 21°-22° C. 1H-NMR (CDCl3)δ7.00 (ddd, 1H), 7.20 (d, 1H, J =5.5Hz), 7.36 (dd,1H), 7.47 (d, 1H, J =5.5 Hz), 7.70 (dd,1H).

1. customequipped with a condenser and a mechanical stirrer
2. customThe apparatus was flushed with nitrogen and about 495 grams of polyphosphoric acid (PPA)
3. additionwas added
4. temperatureto gentle reflux
5. temperaturethe solution was further refluxed for 19 hours
6. customthe organic phase was separated from the PPA
7. extractionthe resulting aqueous phase was extracted with toluene (2×150 ml)
8. dry with materialThe combined organic phases was dried over MgSO4
9. customthe solvents evaporated

ORDレコード

ord-ec2ca4b8ac234ce7a6217d53a9f25181

出典データセット

uspto-grants-1993_01

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US05182279