the triethylamine by anhydrous sodium acetate in the reaction of chlorocoumarin with 2-aminopyridines leads to the formation of the condensed benzopyranopyridopyrimidine system as a result of nucleophilic attack of the amino group by the chlorine atom at position 4.
Keywords: 4-(arylhydrazino)coumarins, 1-aryl-3-(2-hydroxyphenyl)-2H-pyrazin-5-ones, aromatic aldehydes, 2,3-diaryl[1]benzopyrano [4,3-b]pyrazol-4-ones.In a development of work on the synthesis of coumarins with heterocycles at the C(3)-C(4) bond [1-3] we have synthesized pyrazolocoumarins by the reactions of 4-(arylhydrazino)coumarins with aromatic aldehydes. We reverted to pyrazolocoumarins [4-6] which, like other 3,4-heteroannelated coumarins, were observed to have biological activity [7][8][9][10][11][12][13].The reactions of phenyl-, 2-chlorophenyl-and 4-bromophenylhydrazine hydrochlorides with 4-hydroxycoumarin 1 in the presence of triethylamine were carried out by heating in the absent of solvent (1h 30 min, 90-100ºC). In all cases, 1-aryl-3-(2-hydroxyphenyl)pyrazol-5-ones 3a-c were formed along with the corresponding 4-(arylhydrazino)coumarins 2a-c. Pyrazolone 3a was obtained previously [14] by boiling 4-hydroxycoumarin with phenylhydrazine in benzene. On boiling the same reagents in toluene with a catalytic amount of p-toluenesulfonic acid we obtained 4-(phenylhydrazino)coumarin (2a) as the main product (50%) and the pyrazolone 3a in a yield of only 18%. Boiling the pyrazolones 3a-c in acetic anhydride in the presence of p-toluenesulfonic acid gave the diacetyl derivatives 4a-c.The reaction of (4-arylhydrazino)coumarins 2a-c with 4-chlorobenzaldehyde in DMF solution in the presence of equimolar catalytic amounts of piperidine and acetic acid gave the corresponding 2-aryl-3-(4-chlorophenyl)[1]benzopyrano[4,3-b]pyrazol-4-ones 5a-c.
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