الفهرس 
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Abstract
Our starting compound 1-(2,4-dinitrophenyl)-3-(thiophen-2-yl)-1H-pyrazol- 5(4H)-one (1) was synthesized by the reaction of ethyl-3-oxo-3-(thiophen-2- yl)propanoate with (2,4-dinitrophenyl)hydrazine. Scheme 1 The condensation of 1 mole of heterocyclic aldehydes to 1 mole of 5- pyrazolone 1 in acetic acid produced compounds 2a–d, contrarily, using 2 mole of 5-pyrazolone in SDS gave compounds 3a-d. Scheme 2 Furthermore, the treatment of compound 1 with a Reimer–Tiemann reagent offered 1-(2,4-dinitrophenyl)-5-hydroxy-3-(thiophen-2-yl)-1H-pyrazole-4- carbaldehyde (4), followed by condensation with starting pyrazolone 1 gave (Z)-1-(2,4-dinitrophenyl)-4-((1-(2,4-dinitrophenyl)-5-hydroxy-3-(thiophen-2- yl)-1H-pyrazol-4-yl)methylene)-3-(thiophen-2-yl)-1H-pyrazol-5(4H)-one (5). Scheme 3 In addition, the reaction of 5-pyrazolone 1 with formaldehyde in presence of K2CO3 yielded 1-(2,4-dinitrophenyl)-4-(hydroxymethyl)-3-(thiophen-2-yl)- 1H-pyrazol-5(4H)-one (6). Scheme 4 Moreover, the one pot multicomponent reaction (MCR) of 5-pyrazolone 1 with formaldehyde in piperidine and/or different aromatic amines yielded compounds 7 and 8a–c, respectively. Scheme 5 The reaction of compounds 2a-d with malononitrile and/or ethylcyanoacetate and/or cyanoacetamide gives pyranopyrazole derivtives 9a-d, 10a-d and 11ad, respectively. Scheme 6 Compound 6 was treated with different acids to form the esters compounds 12a–c, respectively. These esters reacted with lithium cyclohexylisopropylamide (LICHIPA), followed by the addition of alkyl halide to give α-alkylated esters 13a–c. Moreover, the hydrolysis of these esters with p-toluene sulphonic acid led to the formation of compounds 14a– c. The treatment of compounds 14a–c with thionyl chloride, followed by the addition of optically active R-phenylglycinol yielded the diastereomeric amides 15a–c. Scheme 7 The reaction of compound 14c with thionyl chloride led to formation of (S)- 2-methyl pentanoyl chloride (16). The β-keto ester (17) was synthesized by the reaction of compound 16 with ethyl acetate, while, the reduction of compound 17 to a hydroxy ester 18 was achieved using baker’s yeast. In addition, (S)-18 was reduced to diol compound 19 using LiAlH4 followed by tosylation to give (3S, 4S)-3-hydroxy-4-methylheptyl-4- methylbenzenesulfonate (20). Finally, the tosylated form was converted into compound 21 using ethyl magnesium bromide in the presence of Li2CuCl4. Scheme 8 We used pyranopyrazole compounds 9a-d, 10a-d, 11a-d as key intermediates for the synthesis of skeletons of pyranopyrazole nicotinamide moieties 22a-d, 23a-d, 24a-d by condensation with nicotinic acid in glacial acetic acid. Scheme SScheme 9 Condensation of dimethylformamide-dimethylacetal (DMF˗DMA) with 5- pyrazolone 1 gave enaminone compound 25 followed by reaction with N˗arylsulfonated guanidine under basic conditions to afford fused Pyrazolopyrimidine moieties (26a,b). Scheme 10 The acylation of 5˗pyrazolone 1 with acetyl chloride in presence of Ca(OH)2 gave acetyl pyrazolone 27, which was taken as starting material for synthesis of chalcone derivatives 28a˗d by the reaction with various aromatic aldehydes using ethanolic sodium hydroxide. Scheme 11 Synthesis of novel ring systems of 4-pyrimidylpyrazolones 29a˗d and 30a˗h was carried out via the reaction of guanidine and/or N-arylsulfonated guanidine with different derivatives of ylidene chalcone 28a˗d. Furthermore, the reaction of 4-pyrimidylpyrazolone derivatives 29a˗d with arylsulfonyl chloride gave also compounds 30a˗h. Scheme 12 The reaction of 5-pyrazolone 1 with phenyl isothiocyanate gave the intermediate potassium sulphide salt 31. The latter intermediate reacted with ethyl 2-chloro acetate to give the thioether intermediate 32, which was cyclized spontaneously to thiazole compound 33. Scheme 13 The reaction of thiazole compound 33 with diazonium salt and/or p-nitroso- N,N-dimethylaniline gave azo disperse dyes 34a-d and azomethine dye 35, respectively. Scheme 14 A series of novel azo disperse dyes 36a-d and azomethine dye 37 based on pyrazolone system have been synthesized via the reaction of pyrazolone compound 1 with diazonium salt and/or p-nitroso-N,N-dimethylaniline, respectively. Scheme 15 The mentioned reactions for compounds 2a-d - 11a-d were carried out by traditional conventional heating and ultrasonic irradiation as modern technique in clean organic synthesis; the results of these methods were compared according to time and yield. The structure of all the synthesized compounds was determined by elemental analysis and spectroscopic data including IR, 1H NMR 13C NMR and mass spectral analysis. 1. (S)-4-Methyl-5-nonanol the aggregation pheromone of red palm weevil was efficiently prepared by using compound 6 and used for trapping the red palm weevil. 2. Some newly synthesized compounds 22a, 22d, 23a, 23d, 24a and 24d were screened for their in vitro anti-inflammatory activity by measuring their anti-hemolytic and protein denaturation activities with efficient and simply method. Besides, in vivo anti-inflammatory activity of compound 23d which recorded the best results was investigated, and gave results better than aspirin as a reference drug. 3. Some synthetic target compounds were examined using the agar well diffusion method for their in vitro antibacterial activity. Compounds 30a and 30b exhibited the most potent antibacterial activity against 23 Pseudomonas aeruginosa clinical isolate. 4. In addition, the prepared azo and azomethine dyes were also printed on polyester fabrics and their microbial activity was studied as solid materials and treated textile materials against different types of bacteria two Gram-positive bacteria (Staphylococcus aureus, Bacillus subtilis) and two Gram-negative bacteria (Escherichia coli, Pseudomonas aeuroginosa) and two fungi (Candida albicans, Aspergillus niger).