Pyrazolo quinoxaline preparation

Pyrazolo[3,4-d]pyridazines (555) can be prepared readily from hydrazines and pyrazoles substituted in positions 4 and 5 with an acyl and an ester group, or with two ester groups. 4,5-Pyrazolinediones have been used as starting materials for the synthesis of the quinoxaline derivatives (548) (see above) and of pyrazolo[3,4-e][l,2,4]triazines (556)... 

Lindsley and co-workers developed a general procedure towards the collection of diverse heterocyclic scaffolds from common 1,2-diketone intermediates 96. Substituted quinoxalines 97, fused pyrazolo [ 4,5-g ] quinoxalines 98 and imidazolo[3,4-g]quinoxalines 99 as well as pyrido[2,3-fo]pyrazines 100 and Ihicno[3,4-fo Ipyrazincs 101 have been prepared in excellent yields [132] (Scheme 54), employing optimized reaction conditions (microwave heating of equimolar mixtures of 1,2-diketone 96 and diamine components at 160 °C for 5 min in 9 1 MeOH - AcOH). The use of microwave irradiation resulted in reduced reaction times (5 min vs. 2-12 hours), improved yields as well as the suppressed formation of polymeric species a characteristic of traditional... 

When 4-oxo-5-methyl-lH,4,5-dihydro-l,2,5-benzotriazepine is heated with hydrochloric acid, isomerization occurs with the formation of the N-iminoquinoxaline 4. The structure of this product was demonstrated by reaction with diethyl acetylenedicarboxylate which on hydrolysis and methylation gave the pyrazolo[l,5-a]quinoxaline 5, identical with authentic material prepared from the appropriately substituted phenylpyrazole. ... 

Reaction of 2-chloro 3-substituted quinoxalines 22 with hydrazines provides another simple preparation of pyrazolo[3,4-h]quinoxalines. The parent heterocycle 23 has been obtained by treating the aldehyde 22 (R = CHO) or the dibromomethyl derivative 22 (R = CHBr2) with hydrazine. Similarly the nitrile 22 (R = CN) has given the 3-amino compound 24 in 72% yield, and methylhydrazine with the ester 22 (R = COjEt) gave the 3-hydroxy derivative 25. In spite of the ready cyclization of the aldehyde 22 (R = CHO) with hydrazine, the corresponding... 

---