Quinoline → 4-(2-Nitro-4-trifluoromethylphenylthio)phenol

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Reaction Conditions

Reaction Steps

A mixture containing 12.6 g. (0.10 mole) of 4-mercaptophenol, 7.15 g. (0.05 mole) of copper (I) oxide, and 100 ml. of absolute ethanol is heated at reflux under an atmosphere of dry nitrogen until conversion to the copper thiphenate is complete, as indicated by discharge of the reddish color of the copper (I) oxide. The resultant yellow mixture is cooled to 25°, 27.0 g. (0.10 mole) of 4-bromo-3-nitrobenzotrifluoride, 100 ml. of quinoline, and 10 ml. of pyridine are added, and the reaction vessel is equipped with a Newman still head. The reaction is now slowly heated with concomitant removal of the ethanol to 90° and maintained at this temperature until the conversion is complete, as indicated by vpc techniques. The dark liquid is cooled to 70° C., cautiously poured into 500 ml. of an ice cold 3.0 molar hydrochloric acid solution, and filtered, whereupon the residue is extracted with several portions of ether. the combined ether extracts are washed with a 3.0 molar hydrochloric acid solution, water until neutral, a saturated sodium chloride solution, dried (magnesium sulfate), and concentrated in vacuo to afford a quantitative yield of crude product as a dark solid. Recrystallization foam ether-hexane provides yellow crystals, mp 131°-134° of 4-(2-nitro-4-trifluoromethylphenylthio)phenol. This phenol is then reacted with 2-bromopropionate by the procedure of Example 3 above to provide the desired ethyl 2-[4-(2-nitro-4-trifluoromethylphenylthio)phenoxy]propionate, mp 63°-64° C.

Provenance & Evidence