New ruthenium(II) complexes having a tetradentate ligand such as tris(2-pyridylmethyl)amine (TPA), tris[2-(5-methoxycarbonyl)pyridylmethyl]amine [5-(MeOCO)3-TPA], tris(2-quinolylmethyl)amine (TQA), or bis(2-pyridylmethyl)glycinate (BPG) have been prepared. The reaction of the ligand with [RuCl2(Me2SO)4] resulted in a mixture of trans and cis isomers of the chloro(dimethyl sulfoxide-kappaS)ruthenium(II) complexes containing a TPA or a BPG, whereas a trans(Cl,N(amino)) isomer was selectively obtained for 5-(MeOCO)3-TPA and TQA. The trans and cis isomers of the [RuCl(TPA)(Me2SO)]+ complex were easily separated by fractional recrystallization. The molecular structures of trans- and cis(Cl,N(amino))-[RuCl(TPA)(Me2SO)]+ complexes and the trans(Cl,N(amino))-[RuCl{5-(MeOCO)3-TPA}(Me2SO)]+ complex have been determined by X-ray structural analyses. The reaction of TPA with [RuCl2(PhCN)4] gave a single isomer of the chloro(benzonitrile)ruthenium(II) complex, whereas the bis(benzonitrile)ruthenium(II) complex was obtained with BPG. The cis(Cl,N(amino))-[RuCl(TPA)(Me2SO)]+ complex is thermodynamically much less stable than the trans isomer and isomerizes in dimethyl sulfoxide at 65-100 degrees C. Oxygenation of alkanes catalyzed by these ruthenium(II) complexes has been examined. The chloro(dimethyl sulfoxide-kappaS)ruthenium(II) complexes with TPA and its derivatives using m-chloroperbenzoic acid as a cooxidant showed high catalytic ability. Adamantane was efficiently and selectively oxidized to give 1-adamantanol up to 88%. The chloro(dimethyl sulfoxide-kappaS)ruthenium(II) complex with 5-(MeOCO)3-TPA was found to be the most active catalyst among the complexes examined.
A mixture of 3.6 g. of sodium hydroxide, 5.0 g. of VIIIc, and 30 ml. of dry dimethyl sulfoxide was stirred for 19 hr. at 80-85°. The mixture was cooled, and 100 ml. of ether and 100 ml. of water were added in that order. The phases were separated, and the organic layer was washed successively with 100 ml. of water and 30 ml. of 6 N sodium chloride. The ether solution was distilled, and 3.3 g. of VIIIc was collected. The residue, which was mainly VIIIc, weighed 0.8 g.
Linear polymers containing oxazolidone rings in the main chain were prepared from difunctional urethans and epoxides by the synthetic method previously used for reaction of monofunctional urethans and epoxides. The similarity of the infrared spectra of polymers and model compounds, bisoxazolidones, showed the presence of oxazolidone rings in a polymer chain. The solubility and softening temperatures of the polymers varied with the urethan unit but not with the bisepoxide structure. Polymers prepared from p‐phenylenedimethylurethan and variable bisepoxides were insoluble or partially soluble in dimethylformamide, dimethyl sulfoxide, and m‐cresol and had higher softening temperatures. Polymers from m‐phenylenediethylurethan or toluenediethylurethan and bisepoxides were soluble in the organic solvents mentioned above, and had lower softening temperatures.
Aromatic polydiketopiperazines have been prepared from bis‐2‐chloroacetamides of aromatic diamines in the presence of an epoxide as HCl acceptor and a quaternary ammonium halide catalyst. The structures of the polymers were characterized by infrared and NMR spectra. These polymers were soluble in organic acids such as formic acid, dichloroacetic acid, and trifluoroacetic acid but insoluble in common organic solvents such as dimethylformamide, dimethylacetamide, and dimethyl sulfoxide. Thermogravimetric analysis indicated that these polymers decomposed at 300–340°C.
Bisaminoalcohols were prepared from bisepoxides and ammonia. They were subjected to a polycondensation reaction with dicarboxylic acid chlorides to form polyamides con-ta% hydroxyl groups. These polymers had an inherent viscosity in the range of 0.36 to 1.45 and gave tough, transparent films by solution casting. Polyoxazolines were obtained by treating these polyamides with thionyl chloride.
ZUSAMMENFASSUNG:Bisaminoalkohole wurden aus Bisepoxiden und Ammoniak hergestellt. Sie wurden mit Dicarbonsaurechloriden zu hydroxylgruppenhaltigen Polyamiden polykondensiert. Die Polymeren besitzen eine Viskositatszahl im Bereich von 0,36 bis 1,45 und geben weiche, transparente Filme. Durch Behandlung der Polyamide mit Thionylchlorid wurden Polyoxazoline erhalten. Polyamides Containing Hydroxyl Groups
Preparation of MonomersBisaminoalcohols were prepared by treating bisepoxides with aqueous ammonia in an organic solvent such as acetone, methanol, or dioxane.
NH,\ / \ /
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.