Quinolinecarboxylates

Eu(III) complexes of quinolinecarboxylic acids, including 5, were studied (00MI31). Those of complexes of 5 with Eu(III) and Tb(III) ion were studied, and they were applied for analysis of 5 in medicinal preparations (00UKZ115). Stability of lanthanide complexes with 5 was studied (00MI67). The fluorescence spectra of 5 complexed with Co(II) and ATP was measured (01SA(A)1317). 

CN l-cyclopropyl-6-fluoro-l,4-dihydro-4-oxo-7-(l-piperazinyl)-3-quinolinecarboxylic acid... 

CN ( )-l-ethyl-6,8-difluoro-l,4-dihydro-7-(3-methyl-l-piperazinyl)-4-oxo-3-quinolinecarboxylic acid monohydrochloride... 

C kH,xO 3247-97-2) sec Amitriptyline l-cycIopropyl-6-fluoro-l,4-dihydro-5-mcthyl-7-(3-methyK l-piperazinyl)-4-oxo-3 quinolinecarboxylic acid ethyl ester... 

Fluoro-4-hydroxy-17/-[l,2,4]triazino[4,5- ]quinoline-l,6(2//)-dione 72 was synthesized via the cyclization of the quinolinecarboxylic hydrazide 144 by triphosgene. The hydrazide intermediate 144 was obtained from the corresponding ester 143 (Scheme 16) <2003JHC789>. 

Methyl 2-substituted 4-hydroxyquinoline-3-carboxylates (564) were prepared in 41 -54% yields by heating diazo derivatives (562) in boiling toluene for 0.5-9 hr, via aminomethylenemalonates (563). H-NMR investigation revealed the formation of a 52 48 mixture of aminomethylenemalonate (563, R = COPh) and quinolinecarboxylate (564, R = COPh) when the diazo compound (562, R = COPh) was heated in toluene for 4 hr. A better yield was achieved when the triester (562, R = COOMe) was heated in boiling 1,2-dichlorobenzene (80T1821). 

The thermal cyclization of bis(aminomethylenemalonate) (572) in boiling Dowtherm A for 20 min gave bis(quinolinecarboxylate) (573) in only 4% yield (46JA1264). 

Indolylaminomethylenemalonate (617) was cyclized to pyrrolo[3,2-/i]quinolinecarboxylate (618) in 54% yield by heating in diphenyl ether for 5 min. The dihydro derivative (619, R = H) failed to cyclize under similar conditions, but its 7V-(4-methylphenylsulfonyl) derivative (619, R = 4-MePhS02) gave the expected pyrrolo[3,2-/i]quinoline carboxylate (620) in 44% yield [75JCS(P 1)2409]. 

The isomeric pyrazolo[3,4-/i]quinolinecarboxylate (626) and pyra-zolo[4,3-fi]quinolinecarboxylate (628) were prepared in 80% and 85% yields, respectively, on the cyclization of (4- and 7-indazolylamino)methy-lenemalonates (625 and 627) by heating in Gilotherm at 255°C for 10 min (78GEP2822214 80MI3). 

When the cyclization of compound 807 (R = H) was carried out in boiling phosphoryl chloride, the isomeric chloro derivatives (816 and 817) were obtained in 98% yield. They were separated by the use of column chromatography, in which the linear product (816) was prepared in 50% yield, and the angular product (817) was prepared in 27% yield (74GEP2335760). Earlier, 31% offuro[2,3-j ]quinolinecarboxylic acid (814, R = H) and 7% of furo[3,2-/]quinolinecarboxylic acid (815, R = R1 = H) were isolated from the cyclization of compound 807 (R = H) in phosphoryl chloride and after hydrolysis of the reaction product with hydrochloric acid (71GEP2030899). 

The ring closure of N-( 1,2-benzisothiazol-5-yl)aminomethyIenemalo-nate 1,1-dioxide (852) by heating in diphenyl ether at 250°C gave the linear isothiazolo[5,4-g]quinolinecarboxylate (853) [74JAP(K)75596]. 

The thermal ring closure of AKl,3-benzodithiol-5-yl)aminomethylene-malonate (860) in Dowtherm A at 253-258°C led to a 7.3 1 mixture of 1,3-dithiolo[4,5-g]quinolinecarboxylate (861) and l,3-dithiolo[4,5-/]quinoli-necarboxylate (862) in 81% yield (86M1339). The cyclization of diethyl N-(3,4-dimethylthiophenyl)aminomethylenemalonate under similar conditions afforded only ethyl 6,7-dimethylthio-4-hydroxyquinoline-3-carbox-ylate. 

The cyclization of 2-anthranylaminomethylenemalonate by heating in diphenyl ether gave naphtho[2,1 -/]quinolinecarboxylate (910) in 96% yield (62MI2). 

Indolylaminomethylenemalonates (933) were cyclized by heating in boiling diphenyl ether for 20-40 min to give the angular pyrrolo[3,2-/] quinolinecarboxylates (934) in 56-68% yields (79KGS1084 84MI2). 

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