Thianthrenium perchlorates

Potassium chlorate Metal phosphinates, 4017 Potassium perchlorate, 4018 Sodium 5-azidotetrazolide, 0551 Sodium chlorate Paper, Static electricity, 4039 Sodium chlorate Wood, 4039 Succinoyl diazide, 1438 Tetrakis(chloroethynyl)silane, 2879 Thianthrenium perchlorate, 3455 Triferrocenylcyclopropenium perchlorate, 3885 See other IGNITION SOURCES... 

Tetramethylpyrilium perchlorate, 3167 Tetraperchloratosilicon, 4169 Thianthrenium perchlorate, 3455 Thiotrithiazyl perchlorate, 4032 Triferrocenylcyclopropenium perchlorate, 3885... 

Sterically hindered, mesityl-substituted, stable enols 72 have been examined with regard to one-electron oxidation. Using two equivalents of a one-electron oxidant such as triarylaminium salts, iron(III)phenanthroline, thianthrenium perchlorate or ceric ammonium nitrate in acetonitrile-benzofurans 73 are obtained in good yields within a few seconds [111]. 

Some 5-(alkyloxy)thianthrenium perchlorates (15) have been prepared in which the alkyl group may be primary or secondary. Reaction with iodide ions may result in 5 n2 reaction at the alkyl group or NAr reaction at the sulfonium sulfur atom leading to the formation of thianthrene. ... 

Results of ab initio studies lend support to a mechanism, involving initial formation of Me3C+, CO2 and Me3C0C(0)N=N, proposed to account for oxidative fragmentation of di-tert-butyl azodicarboxylate promoted by thianthrenium perchlorate. ... 

In comparison with hydrocarbons, aromatic amines easily transform into cation radicals. Structures of these cation radicals are well documented on the basis of their ESR spectra and MO calculations (see, e.g., Grampp et al. 2005). The stable cation radical of A/,A,A, A -tetramethyl-p-phenylenediamine (the so-called Wuerster s blue) was one of the first ion radicals that was studied by ESR spectroscopy (Weissmann et al. 1953). The use of this cation radical as a spin-containing unit for high-spin molecules has been reported (Ito et al. 1999). Chemical oxidation of N,N -bis [4-(dimethylamino)-phenyl-A/,A -dimethyl-l,3-phenylenediamine with thianthrenium perchlorate in -butyronitrile in the presence of trifluoroacetic acid at 78°C led to the formation of the dication diradical depicted in Scheme 3.58. 

Combining thianthrene radical ion(l+) with free radicals to produce thianthrenium salts has also been achieved. Decomposition of various cumene hydroperoxides (83MI6) and of azobis(2-phenoxy-2-propane) (85MI1) gave 5-arylthianthrenium ions together with 5-(propen-2-yl)thianthrenium perchlorate in the latter case. 

The preparation of a number of 5-(alkyl)thianthrenium perchlorates has been performed from the thianthrene cation radical with dialkylmercurials and tetraalkyltins (R4Sn) <1983JOC143>. Thianthrene as well as phenoxathiin cation radical perchlorates react with alkenes. The former add stereospecifically to cycloalkenes although the latter afforded a mixture of mono- and bis-adducts in which the configuration of the alkene was retained <2003JOC8910>. 

Various other miscellaneous salts have been used from time to time to initiate cationic polymerisation. These include tris-p-bromophenyl aminium hexa-chloroantimonate (97), anilinium hexafluoroantimonate (98), nitronium tetra-fluoroborate (95), thianthrenium perchlorate (99), and hexachloroantimonate (100), and N-methyl acridinium and N-methylphenazonium salts (75). In general... 

Depending on the amount of thianthrenium perchlorate, /V,/V,/V, /V, /V",/V"-hexakis (anisyl)-l,3,5-triaminobenzene gives its cation radical, dication diradical, and trication triradical as well (Stickley et al. 1997). These species are stable in methylene chloride at low temperatures (at 298 K they can exist for several days). Spin and charge are localized at each oxidized nitrogen atom. The dication diradical and trication triradical structures are ground-state triplet and quartet molecules (Sato et al. 1997). 

The latter two reactions demonstrate the possibility of using thianthrenium perchlorate in preparing magnet-active ion radicals with two or even three unpaired electrons and positive charges. (At this point one very important caution has to be stated Thianthrenium perchlorate is a shock-sensitive explosive solid and should be handled with care.)... 

Thallium triselenimidate , see Thallium 2,4,6-tris(dioxoselena)hexahydrotria-zine-l,3-5-triide, 4756 Thianthrenium perchlorate, 3449 f 3-Thiapentane, see Diethyl sulfide, 1708 1,2,3,4-Thiatriazole-5-thiol, 0385b... 

Tetramethylpyrilium perchlorate, 3161 Tetraperchloratosilicon, 4163 Thianthrenium perchlorate, 3449 Thiotrithiazyl perchlorate, 4026 Triferrocenylcyclopropenium perchlorate, 3879... 

Halo-4-methoxybenzynes are generated by reaction of 5-(3-halo-4-methoxy-phenyl)thianthrenium perchlorates, (20), with LDA in THF their reactions with various /J-aminocarbonyl compounds may give a number of heterocyclic compounds.64... 

A variety of polycyclic A-heterocycles have been synthesised from 5-(3-halo-4-methoxyphenyl)thianthrenium perchlorates 40 by treatment with LDA in the presence of P-amino carbonyl compounds. The reaction involves the generation of 3-halo-4-methoxybenzyne, with thianthrene as the leaving group <05JOC5741>. 

Kim and coworkers have reported a synthetic route to diverse heterocyclic compounds through the nucleophihc addition of P-amino carbonyl compounds 79 to 3-halo-4-methoxybenzynes 78 (Scheme 12.25) [51]. The benzyne intermediate 78 was generated from 5-(3-halo-4-methoxyphenyl)thianthrenium perchlorates 77 upon treatment with lithium diisopropylamide (LDA) in THF at reflux. P-Amino carbonyl compounds, such as P-amino ketones, esters, amides and aldehydes, all react smoothly with benzyne 78 under the reported reaction conditions. Moreover, bis(2-aminophenyl) disulfide, 2-aminophenyl benzenesulfonate... 

The thianthrene cation-radical (56) shows enhanced stability in trifluoro-acetic acid, which is recommended generally as a solvent in which to prepare cation-radicals. Thianthrenium perchlorate (56 C10 as counter-ion) reacts with substituted benzenes PhR at the para position, rapidly where R = MeO, more slowly where R = Me. The product is a sulphonium salt (58). Kinetic studies show that the reaction is second-order in the thianthrene cation-radical (56). The suggested mechanism features the thianthrene dication (57) as the reactive species, formed in low concentration by disproportionation of the thianthrene cation-radical. 

Reactions of 5-(alkoxy)thianthrenium perchlorates with weakly basic nucleophiles Br, P, and PhS in MeCN or DMSO led to 5n2 substitution, E2C elimination, and... 

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