FERROCENE AND ITS DERIVATIVES HAVE BEEN EMPLOYED FOR A VERY LONG TIME AS COMBUSTION CATALYSTS IN PROPELLANT COMPOSITIONS. IT HAS BEEN FOUND THAT THEIR PROPERTIES ARE IMPROVED BY THE ADDITION OF ORGANOSILYL RADICALS BOUND DIRECTLY BY CARBON-SILICON BONDS TO THE CYCLOPENTADIENYL NUCLEUS OF THE FERROCENE. SUCH COMPOUNDS ARE SYNTHESIZED FROM VARIOUS SYNTHETICROUTES, THAT THE MOST IMPORTANT OF THEM IS THE GRIGNARD REACTION [1].2TORGANOSILICON REAGENTS AND COMPOUNDS ARE VALUABLE IN ORGANICSYNTHESIS, SO METHODS TO SYNTHESIZE THEM HAVE BECOME OF CONSIDERABLE IMPORTANCE [2, 3].WE REPORT HERE SYNTHESIS OF 2T1, 1' - BIS [4- (DIMETHYLSILYL) BUTYL] FERROCENE BY A 2TGRIGNARD REACTION FROM1, 1' -BIS (4-CHLOROBUTYL) FERROCENE IN THF.1, 1' -BIS (4-CHLOROBUTYL) FERROCENE WAS PREPARED BY FRIEDEL-CRAFTS ACYLATIONOF FERROCENE WITH 4-CHLOROBUTYROYL CHLORIDE IN DICHLOROMETHANE INTHE PRESENCE OF ALCL3 AS CATALYST. 1, 1' -BIS (4-CHLOROBUTYROYL) FERROCENE WAS REDUCED TO 1, 1' -BIS (4-CHLOROBUTYL) FERROCENEBY NABH4 IN DIGLYME.

IN THIS STUDY WE HAVE INVESTIGATED COMPUTATIONALLY THE MECHANISM OF POLYMERIZATION OF 2, 5-DIBROMO 3-BUTYLTHIOPHENE (1) VIA GRIM METHOD, WITH A FOCUS ON THE ORIGIN OF THE HEAD TO TAIL (HT) SELECTIVITY. TO THIS END, FIRST GRIGNARD REAGENT UNDERWENT OXIDATIVE ADDITION TO MONOMER (1) TO AFFORD THE 2-BROMO-5-CHLOROMAGNESIO-3-BUTYLTHIOPHENE (INTERMEDIATE I1) OR THE 2-CHLOROMAGNESIO 5-BROMO-3-BUTYLTHIOPHENE (INTERMEDIATE I2) REGIOISOMERS. THE MECHANISM OF POLYMERIZATION OF I1 OR I2 WITH NI (DPPP) CL2 [DPPP: 1, 3-BIS (DIPHENYLPHOSPHINO) PROPANE] CATALYST INVOLVES THREE MAIN CATALYTIC STEPS: OXIDATIVE ADDITION, TRANSMETALATION, AND REDUCTIVE ELIMINATION, WHICH WILL BE STUDIED IN THE PRESENT WORK IN MORE DETAIL.

EXPERIMENTAL RESULTS INDICATE THAT THE METAL OF THE CATALYST STRONGLY AFFECTS THE KINETICS OF POLYMERIZATION AND THE REGIOREGULARITY OF SYNTHESIZED POLY-3-ALKYLTHIOPHENES IN M (DPPP) CL2 [DPPP: 1, 3-BIS (DIPHENYLPHOSPHINO) PROPANE] CATALYZED POLYMERIZATION OF 2, 5-DIBROMO-3-ALKYLTHIOPHENE MONOMERS. TO MAKE POSSIBLE ANALYZING SUCH EFFECTS IN MORE DETAIL, WE HAVE COMPUTATIONALLY INVESTIGATED ELECTRONIC STRUCTURE OF MOSTLY KNOWN DPPP INCLUDING CATALYSTS, M (DPPP) CL2, WITH M=NI, PD AND PT. TO THIS END, MOLECULAR STRUCTURE, PARTIAL CHARGE OF ATOMS, HOMO-LUMO ENERGY GAPS (DEHOMO-LUMO), AND THE VALUES OF THE ΡB, L1, L2, L3 AND Ñ2ΡB WERE FULLY DETERMINED BY DFT AND AIM ANALYSIS. RESULTS FROM MOLECULAR STRUCTURE ANALYSIS SHOWED THAT, BY REPLACING NI ATOM WITH PD AND PT, M-CL AND M-P BOND LENGTH INCREASE CONSIDERABLY, WHILE CL-M-CL ANGLE DECREASE SLIGHTLY. FURTHERMORE, DEHOMO-LUMO AND PARTIAL CHARGE ON METAL WERE DECREASED BY THIS ORDER NI<PD<PT. IN ADDITION, NI-P SHOWED LESS ELECTROSTATIC CHARACTERISTIC DUE TO LOWER ΡB, WHICH INDICATES MORE COVALENT CHARACTER OF THIS BOND IN NI (DPPP) CL2 CATALYST IN COMPARE WITH PD-P AND PT-P BONDS IN THEIR CORRESPONDING CATALYSTS.

THE PROTECTION AND DEPROTECTION OF ALCOHOLS IS A COMMON EVENT IN MULTI-STEP ORGANIC SYNTHESES AND TETRAHYDROPYRANYLATION (THP) IS ONE OF THE MOST FREQUENTLY EMPLOYED METHODS. THE THP ETHERS ARE ATTRACTIVE BECAUSE THEY ARE LESS EXPENSIVE, EASY TO DEPROTECT AND ARE STABLE ENOUGH TO STRONG BASIC MEDIA, OXIDATIVE CONDITIONS, REDUCTION WITH HYDRIDES, AND REACTIONS INVOLVING GRIGNARD REAGENTS, LITHIUM ALKYLS AND ALKYLATING AND ACYLATING REAGENTS [1]...

CHIRAL DIAMINES SHOWN BIOLOGICAL ACTIVITY AND SHOWN AN IMPORTANT APPLICATION IN CHEMISTRY AND AS BIDEATATE LIGANDS IN THE ASYMMETRIC SYNTHESIS [1], [2].IN THIS RESEARCH, WE PREPARED IN FIRST TIME THE COMPOUND1 (SCHEME1) FROM THE 4-TBUTYL-2 (NPIPERIDINO METHYL) CYCLOHEXANE [3].GRIGNARD REACTION WITH THIS NITRILE AFFORDED THE FINAL PRODUCT (SCHEME 2). THE STRUCTURE OF THE FINAL PRODUCT WAS CONFIRMED BY IR, 13C NMR, 1H NMR AND MASS.