كاربرد كاتاليزورهاي فلزي در سنتز پروپيلن ايمين، پلي ايميدها و پلي ﴿استر-ايميد﴾ ها به روش كليك و محصول واكنش هاي جفت شدن متقاطع و يكسان

چكيده انگليسي :

175 Application of Metal Catalysts in Synthesis of Propyleneimine Polyimides and Poly ester imide s via Click Coupling and Products of C C Cross and Homo Coupling Reactions Fatemeh Abrishami fatemeabrishami@yahoo com f abrishami@ch iut ac ir January 2013 Department of Chemistry Isfahan University of Technology Isfahan 84156 83111 I R Iran Degree PhD Language Farsi Supervisor Prof A R Hajipour Email haji@cc iut ac ir Abstract In this thesis three different topics were investigated In the first section synthesis of 2 methyl aziridine was investigated Several methods have been developed for synthesis of aziridines For industrial production of aziridine derivatives alkanolamine sulfuric acid esters are cyclized with hot concentrated alkalies in liquid phase Wanker s method This method produces large amounts of inorganic salts and water as by products and has low yield So attempts have been focused on the intramolecular dehydration of alkanolamines in the vapor phase in the presence of catalysts to produce the corresponding alkenimines In this study different catalysts were prepared based on TiO2 and nano TiO2 fumed silica and nano particle SiO2 by addition of cesium and yttrium as promoters then their efficiency on the hydration reaction of isopropanolamine in gas phase were compared Among these catalysts the best catalyst with respect to the highest conversion and selectivity was selected and characterized In the second section new polyimides and poly ester imide s containing triazoles in the main chain were prepared via click coupling These polymers were synthesized by the polymerization of dialkynes including imide linkages with diazides in the presence of Cu I as catalyst in good yields Their thermal stability was evaluated using thermogravimetric TGA analysis under the nitrogen atmosphere and all of them indicated good thermal stability Because of the flexible groups in polymer s backbone they show higher solubility and all of them are soluble in organic polar aprotic solvents such as DMF DMAc DMSO and NMP at room temperature and insoluble in water chloroform methanol and acetone In the third section the synthesis of ortho palladated 2 methoxyphenethylamine and its application in C C cross and homo coupling reactions were studied under both conventional and microwave irradiation conditions The CN orthopalladated complex was applied successfully in the Heck reaction Suzuki reaction homocoupling of aryl halides and cyanation In Heck reaction different aryl halides were coupled with various olefines in NMP as the solvent and K2CO3 as the base at 130 C The best results in Suzuki coupling of aryl halides with aryl boronic acids were obtained in methanol as the solvent and K2CO3 as the base at 65 C Under these circumstances substituted biaryls were produced in excellent yields and short reaction times using catalytic amounts of orthopalladated complex Also an efficient methodology was reported for the preparation of substituted benzonitriles from various aryl halides using this complex as precatalyst and K4 Fe CN 6 The catalytic amount of this catalyst was employed in DMF as the solvent and K2CO3 as the base at 130 C for synthesis of benzonitriles Finally the symmetrical biaryls were obtained via homo coupling reaction of various aryl halides in NMP as the solvent and K2CO3 as the base at 130 C Microwave irradiation led to dramatically reduced reaction times and higher yields in comparison to the conventional reflux conditions Keywords 2 Methyl aziridine nanobased catalysts click reaction ortho palladated complexes coupling reactions microwave irradiation PDF created with pdfFactory trial version www pdffactory com

ابريشمي، فاطمه

كاربرد كاتاليزورهاي فلزي در سنتز پروپيلن ايمين، پلي ايميدها و پلي ﴿استر-ايميد﴾ ها به روش كليك و محصول واكنش هاي جفت شدن متقاطع و يكسان

2-متيل آزيردين , نانو كاتاليزور , واكنش كليك , پليمر , كمپلكس ارتو - پالاديت