86. Cinnolines. Part XXVI. Some 4-cinnolylhydrazines, their preparation and oxidation. Miscellaneous quinoline derivatives

Abstract

4-Cinnolylhydrazine and its 3-chloro-, 6-chloro-, and 6-bromo-derivatives are described. Except for the 3-chloro-compound, these are oxidised by aqueous copper sulphate to the corresponding cinnolines. 4-Phenylhydrazino-and 3-chloro-4-phenylhydrazino-cinnoline have been prepared. Attempts to prepare derivatives of 3-aminocinnoline are mentioned, and miscellaneous quinoline derivatives reported.FROM the reaction between hydrazine and 4-chloroquinaldine Backeberg and Friedmann (J., 1938, 972) obtained either of two products, according to the conditions. Condensation in hot alcohol gave 4-quinaldylhydrazine, whilst reaction a t a higher temperature, under pressure, gave an isomeric compound which the authors suggested to be 3 : 4-diaminoquinaldine. Various pieces of evidence made this structure uncertain, but only after this work had begun was i t completely disproved (Koenigs and Freund, Ber., 1947, 80, 143).Since we desired to prepare 3 : 4-diaminocinnolinesJ in the light of Backeberg and Friedmann's suggestion it seemed _of interest to examine the reaction between 4-chlorocinnolines and hydrazine. Further, 4-cinnolylhydrazines offered the possibility of obtaining, by oxidation, hitherto unknown derivatives of cinnoline unsubstituted a t C,,,.4-Chlorocinnoline reacted with hydrazine in alcohol much more slowly and less vigorously than did 4-chloroquinazoline (Dewar, J., 1944, 619 ; we have repeated the reaction for

Diversity oriented synthesis of 6-nitro- and 6-aminoquinolones and their activity as alkaline phosphatase inhibitors

“…1 (m). MS (GC, 70 eV): m/z (%) ¼ 265 (M + , 1), 225 (23), 224 (11), 223 (71), 186 (33), 185 (12), 184 (100), 178 (11), 148 (15), 140 (10), 138 (28), 113 (21), 110 (29), 109 (70), 81 (32), 79 (47), 75 (26), 74 (16), 66 (22), 63 (14), 53 (30), 43 (33), 41 (42), 39 (19) (12), 262 (11), 244 (16), 236 (10), 223 (16), 198 (12), 186 (36), 184 (100), 178 (10), 148 (13), 140 (12), 138 (31), 123 (14), 113 (19), 110 (21), 95 (55), 80 (19), 79 (16), 75 (19), 74 (12), 67 (34), 66 (18), 63 (10), 55 (40), 53 (14), 41 (36), 39 (15), 29 (28). HRMS (ESI-TOF): calcd for C 14 H 14 ClNO 3 : 279.0656, found: 279.0662.…”

“…13 (m), 1057 (m), 909 (m), 835 (m), 797 (m), 745 (m), 653 (m). MS (GC, 70 eV): m/z (%) ¼ 378 (M + , 57), 377 (55), 363 (12), 349 (15), 293 (100), 287 (20), 280 (73), 247 (57), 204 (15), 177 (24), 131 (26), 57 (14), 43 (20), 41 (23), 29 (16) (28), 248 (13), 247 (58), 234 (10), 204 (14), 177 (24), 131 (20), 43 (29), 41 (18), 29 (10). HRMS (ESI): calcd for C 22 H 25 N 2 O 3 : 364.1782, found: 364.1787.…”

“…MS (GS): m/z (%) ¼ 336 (M À1 , 100), 294 (19), 293 (98), 247 (44), 204 (15), 190 (10), 177 (20), 131 (20), 76 (10), 41 (13), 29 (14) (m), 1014 (w), 964 (w), 924 (m), 914 (w), 847 (m), 824 (s), 798 (s), 746 (s), 700 (w), 672 (w), 653 (m), 576 (w), 542 (m). MS (GS): m/z (%) ¼ 322 (M À1 , 100), 294 (22), 293 (97), 248 (10), 247 (50), 204 (16), 190 (12), 177 (22), 131 (20), 76 (10), 41 (10) (m), 1022 (w), 997 (w), 928 (w), 911 (w), 847 (s), 820 (s), 793 (m), 776 (w), 747 (s), 726 (w), 695 (w), 644 (m), 544 (w). MS (GS): m/z (%) ¼ 322 (M À1 , 72), 323 (16), 281 (19), 280 (100), 252 (14), 234 (38), 206 (12), 205 (13), 204 (17), 191 (18), 190 (17), 115 (10), 43 (30), 41 (16).…”

“…Similar to the rest of the mammalian AP family, TNAP is a homodimeric protein anchored to the cytoplasmic membrane via two GPI moieties. [14][15][16][17][18][19][20][21] A general and modern method for the quinolone synthesis relies on cyclization reactions of ynones. The central core of each subunit consists of an extended β-sheet flanked by α-helices.…”

“…[7][8][9][10][11][12][13] A variety of synthetic strategies have been developed for the synthesis of 4-quinolones. [14][15][16][17][18][19][20][21] A general and modern method for the quinolone synthesis relies on cyclization reactions of ynones. [22][23][24][25] Recently we have developed a synthetic concept for the assembly of several fused 4-pyridones, namely, uorinated 4-quinolones, 26 1,8-naphthyridin-4(1H)-ones, 27 benzo[b] [1,8]naphthyridin-4(1H)ones, 28 pyrido [2,3-b]quinoxalin-4(1H)-ones 28 and thieno [3,2-b]pyridin-4(1H)-ones.…”