الفهرس 
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Abstract
Study the reactivity of α & γ-pyranoquinolinones towards some different reagents
Marwa Mohamed Ahmed
Department of Chemistry, Faculty of Education, Ain Shams University
Alkaline hydrolysis of 3-nitropyranoquinolinones at different reaction times gave at first β-
keto acid, followed by 3-nitroacetylquinolinones, then a mixture of 3-nitroacetylquinolinones and
α-keto acids. By increasing the reaction time the α-keto acids changed to quinoline-3-carboxylic
acids, and finally 4-hydroxyquinolinones were formed. The formation of α-keto acids were
achieved authentically via the conversion of 3-nitroacetylquinolinones to nitroacetyl boron
complexes, then oxidation using selenium dioxide. The reactivity of α-keto acids towards some
nucleophilic reagents was studied. Thus, the treatment of α-keto acid with p-toludiene and
carbothiodihydrazide gave simple condensation products. Also, the reaction between α-keto acid
and some carbon nucleophilic reagents was studied. Where, the reaction of α-keto acid with
chloroacetonitrile gave 1,6-naphthiridine derivatives, while with diethylmalonate yielded 6-alkyl-
2,5-dioxo-5, 6-dihydro-2H-pyrano[3, 2-c]quinoline-3-carboxylic acid ester. The reaction of the
nitro-β-keto acid with thiosemicarbazide produced triazipine derivative, while with hydrazine
hydrate pyrazolo derivative was produced. Treatment of nitro-β-keto acid with triethyl
orthoformate under fusion condition gave 3-nitropyrano[3, 2-c]quinoline-4, 5(6H)-dione. The
condensation cyclization reaction of 3-nitroacetylquinolinone with hydrazine hydrate,
orthophenylene diamine, and guanidine hydrochloride afforded pyrazole, diazepine, and
pyrimidine derivatives. Acetylation of 3-nitroacetylquinolinone, using acetic anhydride produced
acetoxy derivative which cyclized to pyranoquinolinone by the action of PPA. Treatment of
nitropyranoquinolinoe with sulphuryl chloride at 500c, then heating the reaction mixture for 1/2 hr
afforded 3-dichloronitroacetylquinolinone, while, when the latter reaction was carried out at mild
condition, the latter product was formed beside 3-chloro-3-nitropyrano[3, 2-c]quinolinone and
dichloro- β-keto acid were formed. When the pyranoquinolinone was treated with sulphuryl
chloride, the literature product 3-dichloroacetylquinolinone was produced. Acid hydrolysis of
dichloronitroacetylquinolinone, using dichloroacetic acid afforded 3-diketo derivative and α-keto
acid. The reaction of dichloroacetylquinolinone with excess piperidine afforded
dipiperidinylacetyquinolinone, while with piperazine yielded piperazine derivative. The treatment
of dichloroderivative with p-phenylene diamine or p-toludine afforded simple condensation
products. The action of sulphuryl chloride on 4-hydroxyquinolinone afforded 3,3-
dichloroquinolinone, which reacted with malononitrile and afforded acrylonitrile derivative. In the
present work, a combined experimental and theoretical study on molecular structure and
vibrational frequencies of 4-Hydroxy-1-Methyl-3-[2-Nitro-2-Oxoacetyl]-2(1H)Quinolinone
(HMNOQ) was reported. The equilibrium geometries, harmonic vibrational frequencies, thermo-
chemical parameters, total dipole moment and HOMO-LUMO energies are calculated by density
functional theory DFT/B3LYP utilizing 6-311G (d,p) basis set. Results showed that HMNOQ is
highly recommended to be a promising structure for many applications in optoelectronic devices
due to its high calculated dipole moment value (9 Debye) which indicates its high reactivity to
interact with the surrounding molecules. The HOMO-LUMO energy gap of HMNOQ is 4 eV.