Ethyl a-chlorophenylacetate

The partially hydrogenated pyridotriazine 19 was prepared (77AP588) by the dehydrogenation of 18. Alternatively, it was prepared by the reaction of ethyl-a-chlorophenylacetate with the respective lactam followed by reaction with hydrazine. 

Dimethyl-3-phenyl-4-oxothieno[2,3-d]pyrimidine-2-thione (319) reacts with ethyl a-chlorophenylacetate in the presence of anhydrous potassium carbonate in boiling dimethylformamide (DMF)-acteone for 12 hr to give 6,7-dimethyl-2,9-diphenyl-9a-ethoxy-9-oxothiazolo[3,2-fl]thieno [2,3-d]pyrimidin-3(2//)-one (321) in 90% yield [81IJC(B)538] (Scheme 75). The absorption at 1745 cm (five-membered lactam C=0) in addition to that at 1690 cm (six-membered C=0) in the product supports the cyclic structure 321. The formation of 321 must have been through the initially formed unstable mesoionic compound 320, which adds 1 mol of ethanol, liberated during reaction, to afford 321. 

Benzene-1.2-diamine reacts with ethyl a-chlorophenylacetate in the presence of tri-ethylamine to give 3.4-dihydro-3-phenylquinoxalin-2(l/f)-one, which is oxidized to 3-phcnylquinoxalin-2(l//)-one with potassium permanganate or selenious acid in acetic acid. ... 

The reaction of XIII with ethanol affords aniline hydrochloride and ethyl a-chlorophenylacetate (XVII) ( ). 

H. lUhyl a-chlorophenylacetate. Ethyl mandelate (135 g., 0.75 mole) is dissolved in 98 g. (59 ml., 0.82 mole) of thionyl chloride (Note 4) contained in a 500-ml. round-bottomed flask equipped with a rellux condenser capped with a drying tube. The apparatus is allowed to stand in a hood overnight (about 16 hours), at the end of which time the solution is heated under reflux for... 

Chlorophenylacetic acid has been prepared from mandeloni-trile and hydrochloric acid in a sealed tube, from mandelic acid and hydrochloric acid in a sealed tube/ from a-nitrostyrene and hydrochloric acid in a sealed tube, from phenylglycine, hydrochloric acid, and sodium nitrite, from mandelic acid and phosphorus pentachloride (to give the acid chloride which is then hydrolyzed), and, in poor yield, from mandelic acid and thionyl chloride. In the method described, ethyl mandelate is prepared according to Fischer and Speier. The conversion to the chloroester and the acid hydrolysis step are modifications of a preparation described by McKenzie and Barrow. ... 

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