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Abstract ENGLISH SUMMARY SYNTHESIS OF SOME NITROGENOUS HETEROAROMATIC COMPOUNDS: STUDIES ON 2(1H)-QUINOLONE DERIVATIVES: SYNTHETIC ACCESS TO PYRANO[3,2-c] QUINOLINE AND 3-SUBSTITUTED QUINOLINE DERIVATIVES Pyranoquinoline derivatives constitute the parent structure of pyranoquinoline alkaloids which occur in the plant family. They are good synthons for substituted quinolinones which have been of increasing interest since many of these compounds have found useful applications as chemotherapeutic agents. On the basis of the above importance, the present work aim to synthesize a series of pyranoquinoline and 3- substituted quinoline derivatives which are important in the field of organic chemistry. Thus, 2-amino-4-aryl-5-oxo-5,6-dihydro-4H-pyrano[3,2-c]quinolines 6a-f were prepared via reacting arylmethylenemalononitriles 2-c,g with 4- hydroxyquinolines 1a-c or 1e,f in refluxing ethanol containing catalytic amounts of piperidine (cf.Scheme 1). Refluxing 2-amino-4-(2-chlorophenyl)-6-methyl -5-oxo-5,6-dihydro -4Hpyrano[ 3,2-c] quinoline-3-carbonitrile 6d with formic acid or acetic anhydride give 7-(2-chlorophenyl)-5-methyl-5H-pyrimido [5’4’:5,6 ]pyrano[3,2-c] quinoloine-6,8-(7H,11H)-dione 7 and 7-(2-chlorophenyl) -5,10-dimethyl-5Hpyrimido [5’4’:5,6] pyrano[3,2-c] quinoloine-6,8-(7H,9H) -dione 9 respectively(cf.Scheme 2). II ENGLISH SUMMARY Reacting 3-acetyl-1-benzyl-4-hydroxyquinolin-2(1H)-one1d with aryl methylenemalononitiriles 2a,d give 5-amino-4-aryl-2-(1-benzyl-4-hydroxy-2- oxo-1,2-dihydroquinoline-3-yl)-7-imino-7H-pyrano[2,3-b]pyridine-6- carbonitriles 12a,b(cf.Scheme 3) . Compounds 2-acetyl-1-hydroxy-6,7-dihydropyrido [3,2,1-ij] quinolin- 3(5H)-one 1c or1-hydroxy-6,7-dihydropyrido [3,2,1-ij] quinolin-3(5H)-one 1g reacted with arylmethylenemalononitiriles 2e,f to give 11-amino-8-oxo-9- substituted-5,6,8,9-tetrahydro-4H-pyrano[3,2-c] pyrido[3,2,1-ij] quinoline-10- carbonitriles 15a,b(cf.Scheme 4). Reacting 2-acetyl-1-hydroxy-6,7-dihydropyrido [3,2,1-ij]quinolin-3(5H)- one 1c or 1g with ethoxymethylenemalononitrile 16 afford 11-imino -4H, 5H, 6H, 9H-benzo [ij][2,3-b]quinolizin-8-one 18(cf.Scheme 5) . Also, reacting 2-acetyl-1-hydroxy-6,7-dihydropyrido [3,2,1-ij] quinolin- 3(5H)-one 1c or1-hydroxy-6,7-dihydropyrido [3,2,1-ij] quinolin-3(5H)-one 1g with methyl 2-benzolyamino-3-dimethylaminopropionate 19 yield N-(6-(1- hydroxy-3-oxo-3,5,6,7-tetrahydropyrido[3,2,1-ij]quinolin-2-yl)-2-oxo-2Hpyran- 3-yl)benzamide 21 and N-(8,11-dioxo-5,6,8,11-tetrahydro-4H-pyrano[3,2- c]pyrido[3,2,1-ij]quinolin-10-yl)benzamide 22 respectively(cf.Scheme 6) . Condensation of 2-acetyl-1-hydroxy-6,7-dihydropyrido [3,2,1- ij]quinolin-3(5H)-one 1c with aromatic aldehydes afford 2,2’- (arylmethylene)bis(1-hydroxy-6,7-dihydropyrido[3,2,1-ij]quinolin-3(5H)-ones) 28a-d (cf.Scheme 7). The newly synthesized compounds were elucidated by elemental analysis and spectral data. III ENGLISH SUMMARY N O R1 R2 OH R 1 1 R R1 R2 a H C2H5 COCH3 b H CH3 COCH3 c - (CH2)3 - COCH3 d H CH2Ph COCH3 e H C2H5 H f H CH3 H g - (CH2)3 - H CN X 2 R3 2 R3 X a C6H4OPh(m) CN b C6H4Cl(o) CN c C6H4NO2(o) CN d C6H4OH(p) CN e H CN f CH3 CN g C6H4OPh(m) CO2C2H5 IV ENGLISH SUMMARY N O R1 R2 OH N N N N OH O R1 R1 O O R3 NC X COCH3 OH R3 X NC O R1 O NH2 X R3 O R1 CN X CN X 1 a,b O R3 X NH2 R2 = COCH3 R3 = Ar 2 2 R2 = H R3 = Ar 3 4 5 6 H2O - CH3CO2H = R3 R3 6 R1 R3 X a C2H5 C6H4OPh(m) CN b C2H5 C6H4Cl(o) CN c C2H5 C6H4NO2(o) CN d CH3 C6H4Cl(o) CN e CH3 C6H4OPh(m) CN f C2H5 C6H4OPh(m) CO2C2H5 Scheme 1 V ENGLISH SUMMARY N O N O HN N N O CN NHCOCH3 N O N NH CH3 O Ar CN NH2 O Ar O CH3 O CH3 Ar CH3 O Ar O CH3 6 d 9, Ar = C6H4Cl(o) Scheme 2 = 8 7, Ar = C6H4Cl(o) HCO2H (CH3CO)2O VI ENGLISH SUMMARY N N N N O N OH O NH CN R3 NH2 Ph Ph O NH CN O OH R3 OH Ph CH3 O O OH O Ph O R3 CN CN CN CN 1 d 2 b,d 10 11 CH2(CN)2 12 a, R3 = C6H4Cl(o) b, R3 = C6H4OH(p) Scheme 3 -H2 + R3 VII ENGLISH SUMMARY CN CN N N N N N O O OH COCH3 O O R3 CN NC OH O R3 CN NC NH2 CN R3 O COCH3 1 c 13 O OH 1 g 14 15 2 e, f H2O - CH3CO2H a, R3 = H b, R3 = CH3 Scheme 4 R3 CN C2H5O CN N N N N O O O COCH3 NC CN O OH NH CN O O OH COCH3 1 c 1g 16 17 18 H2O - CH3CO2H Scheme 5 - C2H5OH - C2H5OH VIII ENGLISH SUMMARY NHCOPh H3C N CO2CH3 CH3 N N N N N OH O O OH O H3CO2C NHCOPh O OH OH O O O O NHCOPh O NHCOPh O 1c COCH3 19 20 - NH(CH3)2 - CH3OH 21 1f 22 - NH(CH3)2 - C2H5OH Scheme 6 IX ENGLISH SUMMARY N OH O COCH3 ArCHO N N N N N OH O COCH3 N N Ar O O O O O Ar O OH COCH3 Ar HO OH O OH Ar O H3C O O O Ar O N O O N OH Ar OH H2O - CH3CO2H - H2O - CH3CO2H H2O 1 c 23 24 26 25 1 c 27 28 a, Ar = C6H5 b, Ar = C6H4OH(p) c, Ar = C6H4Cl(p) d, Ar = C6H4Br(p) Scheme 7 |