الفهرس 
Structure and propertiesOnly 14 pages are availabe for public view
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Abstract
Synthesis and study the physical properties of some novel quinolinone derivatives
Part I
Chemical reactivity of pyrano[3,2-c]quinoline-3-carboxaldehyde and 3-(ethoxymethylene)-pyrano[3,2-c] quinolinone towards some nitrogen and carbon nucleophiles.
Heating N-methylaniline with two equivalent diethylmalonate gave pyrano[3,2-c]quinolinedione 1 (Scheme 1).
Scheme 1. Formation of pyrano[3,2-c]quinoline-2,5-dione 1.
Thermal condensation of the pyranoquinolinone 1 with triethyl orthoformate was carried out to give the novel 3-(ethoxy methylene)-pyrano[3,2-c]quinolinone 2 (Scheme 2).
Scheme 2. Formation of ethoxymethylene derivative 2.
Acid hydroloysis of compound 2 in boiling (0.01M) acetic acid, afforded the novel pyrano[3,2-c]quinoline-3-carboxaldehyde (3) (Scheme 3).
Scheme 3. Acid hydroloysis of 3-(ethoxymethylene) pyranoquinolinone 2.
The reaction of carboxaldehyde 3 with diethylamine, gave 3-(diethylamino-methylene)pyrano[3,2-c]quinolinone 4. Compound 4 was authentically obtained from stirring of ethoxy methylene derivative 2 with diethylamine in dry toluene (Scheme 5).
Scheme 5. Formation of the enamine 4.
The reaction of carboxaldehyde 3 with hydrazine hydrate gave the corresponding hydrazone derivative 6 (Scheme 6). The latter compound was also prepared directly from treatment of compound 2 with hydrazine hydrate at room temperature, (Scheme 6). Boiling hydrazone derivative 6, in glacial acetic acid, caused annulation to pyrazolo[3’,4’:4,5] pyrano[3,2-c]quinoline derivative 7 (Scheme 6).
Scheme 6. Condensation of ethoxymethylene derivative 2 and carboxaldehyde 3 with hydrazine hydrate.
On the other hand, treatment of compound 2 or 3 with hydrazine hydrate, in boiling DMF gave 4-hydroxy-1-methyl-3-(3-oxo-pyrazole-4-carbonyl)-1H-quinolin-2-one (8) ( Scheme 7).
Scheme 7. Formation of pyrazolone derivative 8.
Similarly, reaction of compound 2 with phenyl hydrazine and hydroxylamine hydrochloride, in boiling DMF, gave (pyrazole-4-carbonyl)quinolin-2(1H)-one 9 and 4-hydroxy-1-methyl-3-(5-oxo-2,5-dihydro-isoxazole-4-carbonyl)-1H-quinolin-2-one (10), respectively. (Scheme 8).
Scheme 8. Reaction of compound 2 with some phenyl hydrazine and hydroxyl amine.
Also, the reaction of compound 8 with hydrazine hydrate, in boiling DMF, afforded pyrazolo[4,3-c]quinolinone 11 (scheme 9).
Scheme 9. Cyclocondensation of compound 8 with hydrazine hydrate.
The guanidine derivative 12 was obtained by stirring of carboxaldehyde 3 with cyanoguanidine, in absolute ethanol, at room temperature. Boiling of a solution of compound 12, in glacial acetic acid afforded primido[4’,5’:4,5]pyrano[3,2-c]quinolin-3-yl)cyanamide 13 (Scheme 10).
Scheme 10. Reaction of carboxaldehyde 3 with cyanoguanidine as 1,3-N, N-binucleophiles.
On the other hand, The reaction of 1,3-binucleophiles with compound 2 in refluxing DMF like cyanoguanidine gave the compound 14 in yield 74% (Scheme 11).
Scheme 11. Reaction of compound 2 with cyanoguanidine
The reaction of compound 2 with malononitrile, was performed, in absolute ethanol, containing few drops of TEA, at room temperature to give the malononitrile derivative 16, (Scheme 12). Boiling compound 16, in glacial acetic acid, gave pyrido[2’,3’:4,5]pyrano[3,2-c]quinoline-2-carbonitrile 17b (Scheme 12).
Scheme 12. Reactivity of compounds 2 and 3 towards malononitrile.
The reaction of carboxaldehyde 3 with 5-methyl-pyrazol-3(2H,4H)-one was carried out, in DMF containing potassium carbonate, to produce (pyrazolyl)-methylenene] pyrano[3,2-c] quinolinone 18 (Scheme 13).
Scheme 13. Condensation of compounds 3 with a cyclic active methylene compound.
Part II
Synthesis and chemical reactivity of 2-formyl-3-(4-hydroxy-1-methylquinoline-3-yl)-3-oxopropionic acid
towards some different nucleophiles.
Stirring ethoxymethylene derivative 2 in (0.25 N) sodium hydroxide solution at room temperature, leading to the novel carboxaldehyde 21 via nonisolable intermediates 19 and 20. (Scheme 14).
Scheme 14. Synthesis of the novel carboxaldehyde 21.
Repeating alkaline hydrolysis of compound 21 in (1N) aqueous sodium hydroxide solutions under reflux for 4h led to the corresponding carboxylic acid derivative 23. Another expected route leading to compound 22 was ruled out on the basis of the spectral data (Scheme 15).
Scheme 15. Alkaline hydrolysis of carboxaldehyde 21 by using (1N) aqueous NaOH.
Cyclocondensation of carboxaldehyde 21 with hydrazine hydrate and phenyl hydrazine, under reflux in DMF, afforded the 3-pyrazolyl quinolinone derivatives 24 and 25, respectively. (Scheme16)
Scheme 16. Reaction of compound 21 with 1,2-N,N-dinucleophiles.
Reaction of carboxaldehyde 21 with guanidine hydrochloride, in boiling DMF, produced (quinolin-3-yl)-pyrimidine-5-carboxylic acid derivative 26 (Scheme 18).
Scheme 18. Rection of compound 21 with guanidine hydrochloride.
Also, treatment of compound 21 with O-phenylendiamine, in refluxing DMF, giving rise to (quinolin-3-yl) benzodiazepine-3-carboxylic acid derivative 27 (Scheme 19).
Scheme 19. Reactivity of carboxaldehyde 21 towards O-phenylendiamine.
Treatment of carboxaldehyde 21 with malononitrile, in refluxing DMF, containing few drops of TEA, gave (quinolin-3-yl)-pyridine-5-carboxylic acid derivative 30 (Scheme 20).
Scheme 20. Reaction of carboxaldehyde 21 with malononitrile.
Similarly, treatment of compound 21 with ethyl cyanoacetate, in DMF, containing few drops of TEA, afforded pyridine-5-carboxylic acid 34 derivative (Scheme 22).
Scheme 22. Reaction of carboxaldehyde 21 with ethyl cyanoacetate.
Part III
Vibrational spectra of 2-Formyl-3-(4-Hydroxy-1-methyl-2-oxo-1,2-dihydro-quinolin-3-yl)3-oxo-propionic acid (FHMQP): Combined experimental and theoretical studies
Experimental and calculated FT-IR spectra for FHMQP at B3LYP/6-311G (d,p).
FHMQP has 31atoms and 87 normal vibrations are distributed as 59Á+28A˝ considering Cs symmetry. Results showed that calculated vibrational frequencies at B3LYP/6-311G (d,p) gives reasonable deviations from the experimental values.
Optimized molecular structure of FHMQP at B3LYP/6-311G(d,p)
Chemical structure of FHMQP compound
FHMQP possesses a high dipole moment value of 9.3 Debye which indicates its relatively high reactivity to interact with the surrounding molecules. FHMQP spin is doublet state which enhances frontier molecular orbitals to split into alpha (spin ↑) and beta (spin ↓) molecular orbitals with two different energy gaps 4.2 and 2.9 eV, respectively. FHMQP is highly recommended to be a more promising structure for many applications in optoelectronic devices such as solar cells.
HOMO-LUMO molecular orbitals for FHMQP at B3LYP/6-311G(d,p).
Any discrepancy noted between calculated and experimental vibrational frequencies may be due to the fact that the calculations have been actually performed on a single molecule in the gaseous state contrary to the experimental values recorded in the presence of intermolecular interactions.