Phosphoric Acid → 5,12-Dihydro-2,9-dimethylquino(2,3-b)acridine-7,14-dione

Participants

Reaction Conditions

Reaction Steps

Two hundred ml of polyphosphoric acid and 100 ml of 85% phosphoric acid are mixed in a mechanically stirred beaker and allowed to cool to 40° C. Thirty grams of 2,5-di(p-tolylamino)terephthalic acid (DTTA) are added in small portions, successively, under intense agitation by Gifford-Wood homogenizer. Care is taken to dissolve each portion before adding another one. The temperature is kept below 60° C. by external water bath cooling. After having dissolved all of the DTTA, as ascertained by dipping a glass rod into the viscous reaction medium and examining for solid particles clinging to the rod, the solution is transferred into a 500 ml round-bottom flask equipped with mechanical stirrer, CaSO4 drying tube, N2 inlet and thermometer, and heated to 100° C. within 45 minutes with stirring. The temperature is held at 100° C. for 45 minutes. The solution develops an orange-brown fluorescense during this time. The solution is poured into 2 l of water with mechanical stirring, generating a dark-colored precipitate. Stirring is continued for 10 minutes. The precipitate is filtered, washed acid-free with water and suspended in 2 l of H2O. The suspension is made basic with a pH of 12 by adding 50 wt % aqueous NaOH solution with stirring, is heated, kept at 60° C. for 15 minutes with continued stirring and filtered while warm. The filter cake is washed with water and dried in a vacuum oven at 70°-80° C. to give 4.0 g (15% yield) of apparently 2,9-dimethylquinacridone by-product. The filtrate and wash water combined are acidified with acetic acid to a pH of 4, with stirring. The resulting red precipitate is filtered, washed acid-free with water and dried overnight at 70°-80° C. under vacuum and slight N2 purge to give 22.3 g (78% yield) of red 2-(p-tolyl)amino-3-carboxy-7-methyl-9(10H)acridinone (TMCA).

Provenance & Evidence