razolo [:~,l-cl]pyri~iiidiiic~ (\.). 'l'h(~ i~cactioiiof' ivitli aiiiiiioiiia aiid vaiioris priiiiary aillilies providrti t l i c corresponding 4-aiiiiiio (T-1) aiid 4-alkylaiiiiiio (1-11 S i derivatives, respectively. Tlic 4-1liercapt.o clcrivat,ive (XI) was synthesized froiii T: a i d thiourca. ' 1 7 1 i ( ~ physical properties aiid cheniical analyses of tlicw coiiipounds appear in Table I. Screeniiig by the Claiicer Cheniotlierapy Sationnl Servicc Clenter has revealed 110 significant aiitiiicoplast,ic activity iii this group thus far. .4 siiniiiiai'y of t'his test data is preseiit,ed in Tahle 11. \7
Experimental.'
4-Cyano-5-trifluoroacetamidopyrazole (II).-Tu 300 nil. ot' ctooled trifluoroacetic anhydride was added in portions with stirriug 5-aniiiio-l-cyariopyra~~~le3 (42 g., (1.39 mole). The mixtiire was heated fur a short time a t 40' and x a s then poured onto flaked ice. Crystallization of tlir resultiiig solid frorii wiitrr provided I1 (73.g., Cll(, i ) as idorless needles, rii.p. 204-21Io3~. Anal. Calcci. for (!6H,F:jS,O: [', ;;>.; r . A. R. Borgmann.
toin. These data indicate I1 to be a significant candidate for further investigation as a urinary tract antibacterial agent. Experimental 2-Furoylformic Acid Semicarbazone.-2-Furoyl cyanide3 (44 g.) was hydrolyzed with concentrat,ed hydrochloric acid to 2furoylformic acid by the method of Fischer.3 The crude acid was dissolved in 50 ml. of ethanol and added to a solution of 44 g. of semicarbazide hydrochloride in 450 ml. of water. The solid semicarbazone was filtered, washed with water, alcohol, and ether. The crude product (40.5 9.) was purified by solution in a mixture of 1500 ml. of water and 100 ml. of concentrated ammonium hydroxide and treating with charcoal. Acidification of the filtered solution gave white, felted needles which were filtered and dried a t 110"; yield 33 g. (46%), m.p. 174' dec. (Fisher-Johns, corrected). An analytical sample was recrystallized from 50% aqueous 2-propanol. Anal. Calcd. for GH,S10,: C, 42.64; H, 3.58; S , 21.32. Found: C,42.79,42.68; H, 3.69, 3.67; ?;, 21.12, 21.25. 6 4 2-Furyl)-as-triazine-3,5(2H,4H)-dione.-2-Furoylformic acid semicarbazone (20 g.) in 450 ml. of propylene glycol was mixed with a sodium ethoxide solution prepared from 7.5 g. of sodium in 150 ml. of absolute ethanol and refluxed for 24 hr. (3) (a) E. Fischer and F. Brauns, Ber., 46, 892 (1913). (b) T o avoid the use of H C N , 2-furoyl cyanide can be conveniently prepared in 4870 yield from t h e acid chloride and cuprous cyanide by the procedure of T. Oakwood and C. Weisgerber for benzoyl cyanide ("Organic Syntheses," Coll. Vol. 111, John \Tiley and Sons, Inc., S e w York, N. Y., 1963, p. 112).
