SYNTHESIS OF SOME NEW SPIROINDOLINE DERIVATIVES INCORPORATED WITH PYRAZOLOHETEROCYCLES

Indole-2,3-dione (1) was treated with malonic acid (2) in a mixture of ethanol/pyridine to afford 1-[3-(2-oxoindolinylidene)]acetic acid (3) . Compound 3 reacted with thionyl chloride to give the corresponding a cid chloride (4). The acid chloride 4 reacted with arenes in the prese nce of AlCl3 to yield 3-(2-oxoindolinylidene)acetophenones 5a-c. Compo unds 5a-c reacted with 3-methylpyrazolin-5-one derivatives 6a,b to giv e 3-aracyl-3-[4'-(3'-methylpyrazolin-5-onyl)]-indo line-2-one derivati ves 7a-f. Compounds 7a-f were treated with phosphorus pentoxide in pho sphoric acid, with ammonium acetate or methanolic methylamine and with phosphorus pentasulfide to give spiro[indoline-3,4'-(pyrazolo[4,5-b]p yran)]-2-ones 8a-f, spiro[indoline-3,4'-(pyrazolo[4, 5-b]-dihydropyrid ine)]-2-ones 9a-f, 10a-f and o(indoline-3,4'-(pyrazolo[4,5-b]thiopyran )]-2-ones 10a-f, respectively. All of the synthesized spiroheterocycle derivatives were identified by conventional spectroscopic methods (IR , H-1 NMR) and elemental analyses. (C) 1996 John Wiley & Sons, Inc.