Decomposition of Alkene Adducts of Thianthrene Cation Radical in Nitrile Solvents. Formation of Alkyl-2-oxazolines and a New Class of Four-Component Products:  5-[(1-Alkoxyalkylidene)ammonio]alkylthianthrenium Diperchlorates

Abstract

The monoadducts (4a-d) of thianthrene cation radical perchlorate (1a) and isobutene, 2-methylbutene, 2-methyl-2-butene, and 2-methylpentene decompose spontaneously in acetonitrile (MeCN) solution, with the formation of thianthrene (Th). Decomposition of 4a (1,2-(5,10-thianthreniumdiyl)-2-methylpropane diperchlorate) and 4a', the corresponding dihexafluorophosphate, was studied in depth and extensively with (1)H and (13)C NMR spectroscopy. Decomposition of 4a was found to involve the solvent itself as well as water in the solvent, remaining from incomplete drying, and gave, apart from Th, successively, the perchlorate salts of 2,4,4-trimethyl-2-oxazoline (6) and 2-amino-2-methylpropyl acetate (7). These salts, 6-HClO(4) and 7-HClO(4), respectively, were prepared and used in understanding the reactions of 4a as well as the relationships among 6, 7, and 2-(acetylamino)-2-methyl propanol (8) in acidified MeCN solution. Decompositions of 4a-d in MeCN and other nitriles (RCN) containing an added alcohol (R'OH) led to new products, 5-[(1-alkoxyalkylidene)ammonio]alkylthianthrenium diperchlorates (5a-u). These compounds were identified with (1)H and (13)C NMR spectroscopy and, in part, with X-ray crystallography and elemental analysis. The mechanisms of formation of 5-7 are discussed.

Efficient Solar Cells Based on an Easily Accessible Diketopyrrolopyrrole Polymer

“…Oxidation experiments were performed under an inert atmosphere with thianthrenium hexafl uorophophate [ 21 ] as the oxidant. Cyclic voltammetry was conducted under an inert atmosphere with a scan rate of 0.1 V s − 1 , using 1 M tetrabutylammonium hexafl uorophosphate in ODCB as the electrolyte.…”

Addition of thianthrene cation radical to non-conjugated dienes—Part II: Addition to two double bonds

“…The preparation of thianthrene cation radical tetrafluoroborate (Th •+ BF − 4 ) and hexafluorophosphate (Th •+ PF − 6 ) and the procedure for drying solvent MeCN have been described earlier [2,4]. All dienes were from commercial sources.…”

“…Under the conditions of reaction, namely, a large molar excess of diene over Th •+ or even a molar ratio diene: Th •+ of 1:2, addition occurred to only one of the diene's double bonds. That is, the diene behaved as an alkene and addition of Th •+ gave the now well-documented mixture of bis-and monoadduct [2][3][4]. The mechanism of the formation of these two adducts has been laid out in Part I.…”

Anodic Oxidation of Ethynylferrocene Derivatives in Homogeneous Solution and Following Anodic Deposition onto Glassy Carbon Electrodes

“…[NBu 4 ][B(C 6 F 5 ) 4 ] was prepared as described earlier and recrystallized from dichloromethane/diethyl ether. The [SbCl 6 ] − and [B(C 6 F 5 ) 4 ] − salts of the thianthrene cation ([C 12 H 18 S 2 ] + ) were prepared as previously described …”

“…The [SbCl 6 ] À and [B(C 6 F 5 ) 4 ] À salts of the thianthrene cation ([C 12 H 18 S 2 ] + ) were prepared as previously described. [27][28][29] Electrochemistry Voltammetry was carried out in cells having a glass-frit separated reference electrode compartment in which a AgCl-coated silver wire was immersed in the same electrolyte used in the working/ auxiliary compartments of the cell. At an appropriate point in the experiment, a small amount of decamethylferrocene (FcH*) was inserted into the working compartment, allowing determination of the potential of [FcH*] 0/ + vs Ag/AgCl in that cell.…”