Direct Asymmetric Michael Additions of Ketones to Nitroolefins and Chalcones Catalyzed by a Chiral C2-Symmetric Pyrrolidine-based Tetraamine

C2-Symmetric pyrrolidine-based tetraamine, available from commercially starting materials, showed good cata- lytic activity for asymmetric Michael additions of ketones to nitroalkenes especially to chalcones. The reactions proceeded to give the corresponding products in good yields and in a highly selective manner.

HETEROAROMATIC POLYMERS—HIGH TEMPERATURE POLYPYRROLONES DERIVED FROM 2,6-BIS(3',4'-DIAMINOPHENYL)-4-BIPHENYLPYRIDINE AND VARIOUS AROMATIC DIANHYDRIDES

A new type of aromatic tetraarnine containing biphenyl moiety in the side chain was synthesized via a modified Chichibabin＇s reaction. 3-Nitro-4-acetamidoacetophenone was reacted with 4-phenyl benzaldehyde in the presence of ammonium acetate to obtain 2,6-bis（3＇,4＇-diaminophenyl）-4-biphenyl pyridine （DPPA）. A series of polypyrrolones （PPys） were prepared using tetraamine and various aromatic dianhydrides via a two-step cyclization procedure. All the PPys show excellent high temperature stabilities with the initial decomposition temperatures of 530-549℃ and residual weight ratio of 49%-80% at 750℃ in nitrogen. The polymers exhibit no apparent glass transition temperatures （Tgs） except PPy-1 （Tg= 327℃）, which is derived from tetraamine DPPA and 2,2-bis[4-（3＇,4＇-dicarboxyphenoxy）-phenyl]propane dianhydride （BPADA）. In addition, the polymers have acceptable mechanical properties with the tensile strength of 65-94 MPa. The PPy films show excellent hydrolysis-resistance in alkaline aqueous medium and could maintain most of the properties even after boiling in 10% aqueous sodium hydroxide solution for a week.

Synthesis and Crystal Structure of a New Mononuclear Nickel(Ⅱ) Mixed Complex Derived from 2-Aminoethyl-bi(3-bi-aminopropyl)amine with 1,10-Phenanthroline

The mixed complex [Ni（L）（L＇）]（ClO4）2 has been synthesized using 2-aminoethyl- bi（3-bi-aminopropyl）amine with phen （1,10-phenanthroline） in the presence of Ni（Ⅱ） ion, and its structure was determined by X-ray diffraction. The crystal crystallizes in monoclinic, space group P21/c with a = 13.713（2）, b = 13.1466（19）, c = 14.780（2） A°, β= 97.620（3）°, V = 2640.9（7） A °^3, F（000） = 1272, Z = 4, Dc = 1.540 g/cm^3, R = 0.0536 and wR = 0.1207. The Ni^2＋ ion is sixcoordinated to furnish a distorted octahedral geometry.

Role of oxygen and ammonium ions in silver leaching with thiosulfate–ammonia–cupric ions

The dissolution of silver with thiosulfate and copper ions was studied in a batch-stirred reactor at 25 °C in the absence and presence of various ammonium ions and oxygen concentrations in the aqueous solution. Leaching silver with 4 mg L-1oxygen in the aqueous solution requires high concentration of ammonium and thiosulfate ions. High silver dissolution is achieved at pH of high cupric tetraamine concentration, around pH 9.8, but a high degradation of thiosulfate ions is resulted from their oxidation by the presence of oxygen. When the oxygen concentration is below 1 mg L-1, dissolved silver thiosulfate species are fairly stable and the degradation of thiosulfate ions in the aqueous solution is low. Under these conditions,high silver dissolution is attained using low thiosulfate concentration. At the oxygen concentration of 4 mg L-1,dissolved silver thiosulfate species precipitate out of the aqueous solution significantly affecting silver dissolution.Precipitation of dissolved silver thiosulfate species occurs because of oxidation of the thiosulfate bonding to the silver.