[reaction: see text] Biologically active 4-aryl-3-alkenyl-substituted quinolin-2(1H)-ones have been synthesized in a short and concise manner employing readily available 4-hydroxyquinolin-2(1H)-ones as intermediates. Key steps in the synthesis include the derivatization of the quinolin-2(1H)-one cores using palladium-catalyzed Suzuki and Heck reactions, installing the 4-aryl and 3-alkenyl substituents. All synthetic transformations (six steps) required for the synthesis of the desired target quinolin-2(1H)-one were carried out using controlled microwave-assisted organic synthesis.

Highly fluorescent and stable 6,7-dimethoxy-2-oxoquinoline-4-carbonitriles (11) were synthesized starting from appropriate 4-hydroxyquinolones 3 via reactive 4-chloroquinolones 8 by using toluenesulfinates as catalysts. In contrast to the well-described 4-trifluoromethyl-substituted analogues 18, N-substituted derivatives 11 fluoresce in water, polar, and apolar solvents in a narrow 430-440-nm window with almost constant quantum yield of 0.5. Equal excitation is possible in the broad double maximum between 385 and 410 nm yield-

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The use of malonates such as diethyl malonates 9, (chlorocarbonyl)ketenes 15 and bis(2,4,6-trichlorophenyl) malonates 18 as reagents for cyclocondensation with 1,3-dinucleophiles to give six-membered heterocycles is described. Further attempts to use malonates such as bis(trimethylsilyl) malonates 19 and bis(carbamimidoyl) malonates 29 as new cyclocondensation agents are described .

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A series of 1,3,6-trisubstituted and 1,3,5,6-tetrasubstituted pyrazolo[3,4-b]pyridines 5 has been synthesized by Friedländer condensation of 5-aminopyrazole-4-carbaldehydes 3 with α-methylene ketones such as acetone (4a) or acetophenones 4b-f with potassium hydroxide as basic catalyst. Condensation of 5-aminopyrazole-4-carbaldehydes 3 and unsymmetric dialkylketones 6 yielded mixtures of isomeric pyrazolo [3,4-b]pyridine derivatives 7 and 8. Condensation of 5-aminopyrazole-4-carbaldehydes 3 with CHacidic acylacetonitriles 9 and acylacetates 11 with piperidine as basic catalyst yielded pyrazolo [3,4-b] [7]. o-Aminoaldehydes are the key intermediates for the synthesis of various biologically active heterocycles e.g. [8,9] using the Friedländer reaction with ketones in a 4+2 cyclocondensation [10], which prompted us to investigate the reaction pathway of 5-aminopyrazole-4-carbaldehydes with α-methylene ketones to new 1,3,6-trisubstituted and 1,3,5,6-tetrasubstituted pyrazolo [3,4-b]pyridines, especially to 1,3,6-triarylpyrazolo[3,4-b]pyridines. A literature survey shows a few reports on the synthesis of pyrazolo [3,4-b]pyridines using the Friedländer condensation [11], however with substitution patterns different to ours.The required starting materials for the intendedFriedländer condensation, 5-aminopyrazole-4-carbaldehydes 3, were synthesized by cyclocondensation of p-substituted aroylacetonitriles, a class of compounds which was studied recently by us for other cyclization reactions [12]. p-Substituted aroylacetonitriles cyclize as 1,3-dicarbonyl synthons with arylhydrazines already on heating without catalysts according to known methods [13] and furnished in good to excellent yields 5-aminopyrazoles 1, which afforded on Vilsmeier-Haack formylation with excess dimethylformamide and phosphoryl chloride 4-formyl-pyrazolyl-dimethylimidoformamides 2. Thermal analysis of formamides 2 by differential scanning calorimetry (DSC) revealed that they are thermally stable compounds which showed thermal decomposition only above 350 °C. Hydrolysis of formamides 2 with refluxing ethanolic sodium hydroxide yielded the required 5-aminopyrazole-4-carbaldehydes 3 in good yield.

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