Bridged reduction

In 1972, Chinese researchers isolated, by extraction at low temperature from a plant, a crystalline compound that they named qinghaosu [the name artemisinin (la) is preferred by Chemical Abstracts, RN 63968-64-9]. The plant source of artemisinin is a herb, Artemisia annua (Sweet wormwood), and the fact that artemisinin is a stable, easily crystallizable compound renders the extraction and purification processes reasonably straightforward. The key pharmacophore of this natural product is the 1,2,4-trioxane unit (2) and, in particular, the endoperoxide bridge. Reduction of the peroxide bridge to an ether provides an analogue, deoxyartemisinin 3, that is devoid of antimalarial activity. ... 

Stoddard and co-workers [45-47] describe the synthesis of cyclic and linear ribbon-type oligomers starting from the monomers 21 [39] and 23 [42]. The double stranded macrocycles, e.g. 27, generated are intermediates in the preparation of cyclic oligoarenes (cycloacenes) - attractive compounds with two dimensional cyclic J7-systems of the Huckel-type. Synthetic approaches to remove the oxo-bridges reductively and to generate the final fully unsaturated hydrocarbons, lead only to intermediates, e.g. 28, which are partially hydrogenated [46]. 

Inner-sphere mechanism. " For stoicheioraetry see text. At 0 °C. Inner-sphere mechanism double bridging. Reductant is chromium(ii) monomer in acetate buffer, average composition Cr(OAc)2. f At30°C. Data at 7=4.0 mol 1 are also reported. There is also a Cr +-independent aquation term in the rate law. The only detectable Cr product is [Cr(H20)6] + however, an inner-sphere mechanism is suggested, the primary product undergoing rapid aquation, l When [H+] >0.2 mol 1" the order in chromium(ii) decreases. Chromium(ni) product contains 5-bonded thiocyanate. 

While Eq. III-18 has been verified for small droplets, attempts to do so for liquids in capillaries (where Rm is negative and there should be a pressure reduction) have led to startling discrepancies. Potential problems include the presence of impurities leached from the capillary walls and allowance for the film of adsorbed vapor that should be present (see Chapter X). There is room for another real effect arising from structural peiturbations in the liquid induced by the vicinity of the solid capillary wall (see Chapter VI). Fisher and Israelachvili [19] review much of the literature on the verification of the Kelvin equation and report confirmatory measurements for liquid bridges between crossed mica cylinders. The situation is similar to that of the meniscus in a capillary since Rm is negative some of their results are shown in Fig. III-3. Studies in capillaries have been reviewed by Melrose [20] who concludes that the Kelvin equation is obeyed for radii at least down to 1 fim. 

Two synthetic bridged nitrogen heterocycles are also prepared on a commercial scale. The pentazocine synthesis consists of a reductive alkylation of a pyridinium ring, a remarkable and puzzling addition to the most hindered position, hydrogenation of an enamine, and acid-catalyzed substitution of a phenol derivative. The synthesis is an application of the reactivity rules discussed in the alkaloid section. The same applies for clidinium bromide. 

An additional benefit of prethickening is reduction in cake resistance. If the feed concentration is low, there is a general tendency of particles to pack together more tightly, thus leading to higher specific resistances. If, however, many particles approach the filter medium at the same time, they may bridge over the pores this reduces penetration into the cloth or the cake underneath and more permeable cakes are thus formed. 

Disulfides. As shown in Figure 4, the and h-chains of insulin are connected by two disulfide bridges and there is an intrachain cycHc disulfide link on the -chain (see Insulin and other antidiabetic drugs). Vasopressin [9034-50-8] and oxytocin [50-56-6] also contain disulfide links (48). Oxidation of thiols to disulfides and reduction of the latter back to thiols are quite common and important in biological systems, eg, cysteine to cystine or reduced Hpoic acid to oxidized Hpoic acid. Many enzymes depend on free SH groups for activation—deactivation reactions. The oxidation—reduction of glutathione (Glu-Cys-Gly) depends on the sulfhydryl group from cysteine. 

Conformal coatings are protective coatings appHed to circuit board assembHes. They protect the interconnect conductors, solder joints, components, and the board itself they reduce permeabiHty to moisture, hostile chemical vapors, and solvents in the coating. Use of conformal coatings eliminates dendritic growth between conductors, conductor bridging from moisture condensation, and reduction in insulation resistance by water absorption. 

H2 or O2 from water in the presence of a sacrificial reductant or oxidant employ a mthenium complex, typically [Ru(bipy)2], as the photon absorber (96,97). A series of mixed binuclear mthenium complexes having a variety of bridging ligands have been the subject of numerous studies into the nature of bimolecular electron-transfer reactions and have been extensively reviewed (99—102). The first example of this system, reported in 1969 (103), is the Creutz-Taube complex [35599-57-6] [Ru2(pyz)(NH3. 

Rhenium Halides and Halide Complexes. Rhenium reacts with chlorine at ca 600°C to produce rheniumpentachloride [39368-69-9], Re2Cl2Q, a volatile species that is dimeric via bridging hahde groups. Rhenium reacts with elemental bromine in a similar fashion, but the metal is unreactive toward iodine. The compounds ReCl, ReBr [36753-03-4], and Rel [59301-47-2] can be prepared by careful evaporation of a solution of HReO and HX. Substantiation in a modem laboratory would be desirable. Lower oxidation state hahdes (Re X ) are also prepared from the pentavalent or tetravalent compounds by thermal decomposition or chemical reduction. 

Furthermore, carehil carbonylation of the dimer produces [Cp 22 (CO)]2N which on protonolysis gives no reduced form of N2, iadicatiag that both bridging and terminal N2 are required for reduction (249). 

CH2SH + 1/2 O2 -CH2-S-S-CH2 + H2O This reaction requires an oxidative environment, and such disulfide bridges are usually not found in intracellular proteins, which spend their lifetime in an essentially reductive environment. Disulfide bridges do, however, occur quite frequently among extracellular proteins that are secreted from cells, and in eucaryotes, formation of these bridges occurs within the lumen of the endoplasmic reticulum, the first compartment of the secretory pathway. 

The iodide-induced reduction is essentially the reverse of a halogenation. Application of the principle of microscopic reversibility would suggest that the reaction would proceed through a bridged intermediate as shown below. ... 

Exhaustion The state in which the adsorbent is no longer capable of useful ion exchange the depletion of the exchanger s supply of available ions. The exhaustion point is determined arbitrarily in terms of (1) a value in parts per million of ions in the effluent solution and (2) the reduction in quality of the effluent water determined by a conductivity bridge which measures the resistance of the water to the flow of an electric current. 

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