Aprotic oxidizing agents

Davis, F. A., Jenkins, R., Jr., Yocklovich, S. G. 2-Arenesulfonyl-3-aryloxaziridines a new class of aprotic oxidizing agents (oxidation of organic sulfur compounds). Tetrahedron Lett. 1978,5171-5174. 

It can also be used as a mild aprotic oxidizing agent (soluble in all common organic solvents), for the transformation of sulfides into the corresponding sulfoxides.phosphines into phosphine oxides, in the oxidation of alcohols to aldehydes (as co-oxidant of CrOs Py), in the Baeyer-Villiger reaction (in the presence of TfOSiMes). It has also been employed in the transformation of acetylenes to the corresponding lodoacetylenes. ... 

Cross-hnked polyacrylamides are a group of hydrophihc solid supports introduced primarily for preparation of biopolymers (Fig. 4). Unhke PS resins, polyacrylamides have excellent swelling capacity in both protic (water, alcohols) and aprotic (dichloromethane, dimethylformamide) solvents [88]. These beads are stable towards bases, acids, and weak reducing and oxidizing agents [89]. Predictably, conditions under which amide bonds are cleaved (i.e., sodium in liquid ammonia) [90] lead to rapid decomposition of the polymer. 

Due to the limited extent of this paper, we mention only some positive results achieved in the orientation to two main directions i.e. to oxidative principles and to alcoholates in aprotic solvents. The research of oxidative principles (see e.g. [9]), involved the use of compounds with active chlorine, active iodine, peroxo-compounds, various mixtures of these compounds, as well as the use of oxidative agents with enhancing solubility and thus decontamination efficiency by adding detergents. It can... 

Alkali periodates (in aqueous solution)646 and ammonium periodate (in anhydrous aprotic solvent),647 when applied in the presence of a catalytic amount of 0s04, are selective oxidizing agents used to form carbonyl compounds. Os04 apparently transforms the alkene to an 1,2-diol that is subsequently cleaved by the periodate to the carbonyl compound end products. The periodate also serves to regenerate Os04. 

More recently, (26) salts of para-bromophenols have been reacted with a variety of oxidizing agents as initiators under anhydrous conditions in the presence of aprotic, dipolar solvents. Under these conditions it is remarkable that the product from 2,6-dichloro-4-bromophenol appears to be the high molecular weight, linear 1.4-phenylene ether (VI). 

Chichibabin amination refers to a reaction in which a hydrogen of an azaheteroarene is replaced by an amino group. The reaction is usually carried out by heating the heterocycle with a metal amide at elevated temperatures in an aprotic inert solvent. Potassium amide or sodium amide in liquid ammonia have also been found to be appropiate reagents for amination the presence of an oxidant seems to promote the reaction. Potassium nitrate is usually employed as an oxidant, 9 16 but other work shows that potassium permanganate can also successfully be used as an oxidizing agent in liquid ammonia.IO-20 17... 

Oxidation of Sulfides (Section 11.12C) Oxidation of a sulfide gives either a sulfoxide or a sulfone, depending on the oxidizing agent and experimental conditions. Air oxidation of dimethyl sulfide is a commercial route to dimethyl sulfoxide, a polar aprotic solvent. 

Pd(OAc)2 in AcOH at 120 C for 2 h] (62) were not suited for this preparation. However, the compound 131 was obtained in 74-85% yield when the reaction was carried out in die presence of sodium hydrogoi carlwnaie and chloranil as an oxidizing agent in an aprotic solvent, such as 1,2-dkhloroethane or 1,2,4-trichlorobenzene. Asymmetric reduction in the presence of a rhodium-complex as catalyst afforded the 4-bromotryptophan 133 (Scheme 51). 

A convenient agent for the preparation of perfluoroalkene epoxides is sodium hypochlorite in a mixture with aqueous acetonitrile or another aprotic solvent cis-and tr<3 5-perfluoroalkenes are oxidized with retention of configuration [9, 10, 11, 12 13] (equation 7, Table 1)... 

Keywords chemical warfare agents, decontamination, detoxification, human skin, chemisorption, oxidation, detergents, alcoholates, aprotic solvents... 

Nitronium salts are efficient and powerful nitrating agents. Nitronium tetrafluoroborate is the most commonly used nitronium salt for nitration and is commercially available as a solid or as a solution in sulfolane in which the ions are highly solvated and exist as an ion pair. Nitronium tetrafluoroborate shows poor solubility in most organic solvents and so the more soluble nitronium hexafluorophosphate is sometimes preferred for nitrations. Olah and co-workers - have studied the nitration of a vast array of aromatics with nitronium salts. Solutions of nitronium salts in aprotic organic solvents are useful for the nitration of acid sensitive or readily oxidized substrates. Nitronium tetrafluoroborate has been used for the... 

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