Oxidation of substituted hydrazines by superoxide ion: the initiation step for the autoxidation of 1,2-diphenylhydrazine

Long term stability of superoxide ion in piperidinium, pyrrolidinium and phosphonium cations-based ionic liquids and its utilization in the destruction of chlorobenzenes

“…O ÁÀ 2 has been used in many applications such as reduction of sulfur dioxide (SO 2 ) in DMF [31], reduction of elemental sulfur in DMSO [32]; nucleophilic oxygenation of CO 2 to form the peroxydicarbonate C 2 O 2À 6 species [33,34]; electrosynthesis of H 2 O 2 [27,35]; reaction with vitamin K 1 and its related compounds in the presence of crown ether to produce the corresponding 2,3-oxide and phthalic acid [36]; reaction with 3,5-di-tert-butylcatechol (DTBCH 2 ), ascorbic acid, dihydrophenazine, and dihydrolumiflavin to produce their respective anion radicals [37]; reaction with 1,2-disubstituted hydrazines to produce the anion radical of the 1,2-disubstituted azo compound [38]; oxidation of primary and secondary alcohols to the corresponding carboxylic acids and ketones respectively [39][40][41] [43] who found that the generated O ÁÀ 2 was unstable, thus could not be utilized in reactions. AlNashef et al (2001,2002) were the first group to prove that generation of stable superoxide can be done in the imidazolium based ILs (ImILs) [27,44].…”

Electrochemical reduction of dioxygen in Bis (trifluoromethylsulfonyl) imide based ionic liquids

“…Many studies have been done on applications of O ÅÀ 2 such as destruction of polyhalogenated aromatic hydrocarbons (e.g., PCB's and HCB) [63,34,20], dichloroethene, trichloroethene, and tetrachloroethene in DMF or acetonitrile [11]; reduction of sulfur dioxide (SO 2 ) in DMF [42], reduction of elemental sulfur in DMSO [45]; nucleophilic oxygenation of carbon dioxide to form the peroxydicarbonate C 2 O 2À 6 species [52,13]; reaction with vitamin K 1 and its related compounds in the presence of crown ether to produce the corresponding 2,3-oxide and phthalic acid [55]; reaction with 3,5-di-tert-butylcatechol (DTBCH 2 ), ascorbic acid, dihydrophenazine, and dihydrolumiflavin to produce their respective anion radicals [57]; reaction with 1,2-disubstituted hydrazines to produce the anion radical of the 1,2-disubstituted azo compound [10]; oxidation of primary and secondary alcohols to the corresponding carboxylic acids and ketones respectively [61,1].…”

Base (O.-2, e-, or OH-)-induced autoxygenation of organic substrates: a model chemical system for cytochrome P-450-catalyzed monoxygenation and dehydrogenation by dioxygen.

“…PhNNPhO + 02 -fast PhN=NPh + 0-2 [3] The sum of these two reactions represents an 0,--initiated autoxidation of a donor molecule (PhNHNHPh) and the activation of 02 to H202 Analogous results have been observed for other 1,2-disubstituted hydrazines, dihydrophenazine, and dihydro-3-methyllumiflavin (9). All of these donor systems constitute models for the reduced flavoproteins that provide the two reducing equivalents of the cytochrome P-450 02-activation cycle (see reaction 1) (1).…”

“…The rationale for the design of this model system is based on the results of two recent investigations (9,10). In the first of these, it was found that 0°-(as well as other strong bases) initiates the autoxidation of 1,2-disubstituted hydrazines in aprotic media.…”