Extrusion controlled oxidation

Electron-deficient alkenes add stereospecifically to 4-hydroxy-THISs with formation of endo-cycloadducts. Only with methylvinyl-ketone considerable amounts of the exo isomer are produced (Scheme 8) (16). The adducts (6) may extrude hydrogen sulfide on heating with methoxide producing 2-pyridones. The base is unnecessary with fumaronitrile adducts. The alternative elimination of isocyanate Or sulfur may be controlled using 7 as the dipolarenOphile. The cycloaddition produces two products, 8a (R = H, R = COOMe) and 8b (R = COOMe, R =H) (Scheme 9) (17). Pyrolysis of 8b leads to extrusion of furan and isocyanate to give a thiophene. The alternative S-elimi-nation can be effected by oxidation of the adduct and subsequent pyrolysis. 

Waghorn, P. E., The Control of Oxidation and Odour in Extrusion Coating, ... 

The dinuclear complex tru 5-[(NO)(py)4Ru(//-CN)Ru(py)4(CN)] has been prepared and spectroscopically characterized. Photoinduced extrusion of NO occurs when the complex is irradiated at the donor-acceptor CT band. Electronic coupling in the complex is discussed, as well as the results of controlled potential reduction (of NO) and oxidation (of Ru in the dicyano chromo-phore). " Bridging NO ligands are observed in [(acac)2Ru(/u-NO)2Ru(acac)2] which formally possesses a Ru2(NO)2 " " core. The complex exhibits two one-electron reductions (one reversible and the other irreversible) and an irreversible two-electron oxidation in which decomposition to cw-[Ru(NO)(MeCN)(acac)2] occurs. ... 

Thermal extrusion of a sulfur atom is the most common thermal reaction of a thiepin. The mechanism of this thermal process involves two orbital symmetry controlled reactions (69CC1167). The initial concerted step involving a reversible disrotatory electrocyclic rearrangement is followed by a concerted cheleotropic elimination of sulfur (Scheme 29). Similar aromatization reactions occur with thiepin 1-oxides and thiepin 1,1-dioxides, accompanied by the extrusion of sulfur monoxide and sulfur dioxide respectively. Since only a summary of the major factors influencing the thermal stability of thiepins was given in Section... 

Within the last decade we have obtained a tentative concept of the molecular basis for this mammalian mitochondrial thermogenesis, and we know that in contrast to the thermogenic plant mitochondria, substrate oxidation in brown adipose tissue mitochondria is basically energy conserving, with proton extrusion occurring [5], with respiratory control, and with an ability, in principle, to capture the chemical energy in the form of ATP. 

Poly Ethylene Oxide) (PEO) Polymers. In the same family as PEG, but having higher molecular weights are POLYOX resins, which are water-soluble polymers. Because of their low melting point and unique swelling properties, coupled with the controlled rate of dissolution, POLYOX resins have been used to make sustained-release formulations by hot-melt extrusion.f ... 

The essential role of cytochrome c release from injured mitochondria in the activation of caspase 9 has been alluded to above. This pathway is especially important in proapoptotic stimuli that are not initiated by surface receptors for apoptosis, such as UV irradiation, and may involve mitochondrial dependent pathways [83]. Continued respiration in the presence of an open mitochondrial pore may result in the generation of reactive oxygen species. Release of cytochrome c may be mediated by the opening of the mitochondrial FT pore, a non-selective channel whose composition is only partially defined [84]. Inhibitors of FT pore opening, such as cyclosporine, which binds to the adenine nucleotide translocator (ANT), a component of the FT pore, and bongkrekic acid, as well as Bcl-2, prevent cytochrome c release and inhibit apoptosis [85] whereas activators of the FT pore, such as atractyloside and Bax induce it [86]. Oxidants can rupture the outer membrane of mitochondria and release caspase-activating proteins [87]. Some studies have shown cytochrome c release before collapse of the mitochondrial membrane potential [83] suggesting alternate control of the FT pore. Many, but not all, of the members of the Bd-2 family of proteins reside in the inner mitochondrial membrane, form ionic channels in hpid membranes and increase rates of proton extrusion in mitochondria [88] and thus may control the FT pore. The antiapoptotic and mitochondrial affects of Bd-2 are independent of caspase activity as they occur in the presence of caspase inhibitors and also in yeast that lack caspases [86]. 

This work shows the acquired experience in the preparation at pilot-scale of a novel propane ammoxidation catalyst based on a partially nitrided V-Al mixed oxide obtained hy co-precipitation. A systematic investigation of the different parameters controlling the preparation of the catalyst via a co-precipitation route at different scales was carried out. At lab-scale (50 to 100 g), the preparation parameters optimized were precipitation pH, V/Al atomic ratio, V concentration in solution and nitridation conditions, while at pilot-scale (1 kg), the optimized parameters were precipitation and ageing time, solution/solid ratio during the washing step, drying and calcination conditions, and extrusion parameters. Our results show that the optimum preparation conditions for the VAION system are pH = 5.5, V/Al atomic ratio = 0.25, concentration of V species in solution = 30.10 M. This catalyst shows the highest selectivity and yield in acrylonitrile. The samples prepared at different scales show the same activity profile in the propane ammoxidation reaction. 

Extrusion of sulfur dioxide from oxidized thiophene derivatives is an exceptional method to prepare cis-dienes as components for Diels-Alder reactions. An example of this approach utilizes the Diels-Alder reactivity of the furan ring in substituted 4//,6ff-thieno[3,4-c]furan-3,S-dioxides to react with a variety of dienophiles such as DMAD, dimethyl maleate and dimethyl fumarate which then lose SO2 to form another reactive diene (Eq. 17) <94H961>. A review of the preparation and use of 4i/,6f/-thieno[3,4-c]furan-S,5-dioxides as well as other heteroaromatic-fused 3-suIfolenes is report <94H1417>. The preparation of dihydrothienooxazole 80 requires the careful control of the reaction time and temperature as well as the reactants molar ratio <94JOC2241>. Specific control of the alkylation conditions for 81 (X = COCH3) allows for the preparation of either 1,4-disubstituted or 1,6-disubstituted 4, 6//-thieno[3,4-c]furan-S,S-dioxides. These molecules could be used as intermediates for the preparation of novel pentacyclic compounds <94JCS(P1)1371>. 

There are a variety of reasons for the use of additives in a resin, including (1) to improve the processing conditions, (2) to increase the resin s stability to oxidation, (3) to obtain better impact resistance, (4) to increase or decrease hardness, (5) to control surface tension, (6) to facilitate extrusion and molding, (7) to control blocking, (8) to reduce cost, and (9) to increase flame resistance. 

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