Ion radicals. XVIII. Reactions of thianthrenium perchlorate and thianthrenium trichlorodiiodide

Murata, Y.; Shine, Henry J.

doi:10.1021/jo01263a034

Cited by 121 publications

(63 citation statements)

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“…Given the apparent success of electrochemical generation of diazenium 6 , we were keen to test whether we might be able to chemically oxidize radical 10 to diazenium 6 in solution. We selected thiathrenium perchlorate, 14 , as a suitable one-electron oxidant because of its ready solubility in acetonitrile and the ease with which the reduced thianthrene form could be separated from our expected products …”

Section: Resultsmentioning

confidence: 99%

Intermediacy of a Persistent Urazole Radical and an Electrophilic Diazenium Species in the Acid-Catalyzed Reaction of MeTAD with Anisole

Breton

Suroviec

2015

J. Org. Chem.

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The reaction of N-methyl-1,2,4-triazoline-3,5-dione (MeTAD) with anisole in the presence of trifluoroacetic acid affords unexpected disubstituted urazole products instead of the expected monosubstituted urazole as typically observed in the reactions of MeTAD with other substituted benzenes. Our investigation into the mechanism of formation of these disubstituted products suggests that MeTAD is capable of further reaction with the initially formed monosubstituted urazole to afford a persistent urazole radical. The identity of this radical has been established by UV-vis spectroscopy, the nature of its self-dimerization reaction, and via independent generation. Electrochemical oxidation of this radical was carried out, and the resulting diazenium ion was demonstrated to be reactive with added substituted benzenes, including anisole. When oxidation was carried out chemically using thianthrenium perchlorate in the presence of anisole it was shown to produce the same disubstituted products (and in the same ratio) as observed in the acid-catalyzed reaction. A common diazenium species is proposed to be active in both cases. We also report the synthesis and characterization of three interesting tetrazane dimers resulting from unstable urazole radicals.

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Section: Resultsmentioning

confidence: 99%

Intermediacy of a Persistent Urazole Radical and an Electrophilic Diazenium Species in the Acid-Catalyzed Reaction of MeTAD with Anisole

Breton

Suroviec

2015

J. Org. Chem.

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“…)~~~~~l~o~ ~g(oep')(oclo3)]2 1 2 Scheme 1. Formation of dimers ofn-cation radicals: a) oxidation with thianthrenium perchlorate [6] (1 : 1.05) in CHZCI,; crystallization from b) CH,CI,/CHCI, (Sjl) and hexane or c) toluene/CH,C1, (4/1) and hexane. Dried solvents and flame-dried glassware must be used throughout to avoid acid-catalyzed demetalation [7].…”

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confidence: 99%

Inter‐Ring Interactions in Dimers of Magnesium π‐Cation Radicals: Control by Solvent Polarity

Brancato‐Buentello

Scheidt

1997

Angew. Chem. Int. Ed. Engl.

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COMMUNICATIONSgreen solution was vigorously stirred under an oxygen overpressure (ca. 1 bar, 12 h) . After allowing the mixture to cool to room temperature, phase separation of the solvent system occurred immediately. The precipitated p-chlorobenzoic acid (6a) was filtered off and recrystallized from acetonitrile affording a white solid (0.68 g, 4.3 mmol, 87% yield, mp 240-243°C). The green perfluorinated phase containing the catalyst was separated from toluene and can be used for further experiments. Preparation of cyclooctene oxide (11 a). A 25 mL flask was charged with a solution of the ruthenium catalyst 4b (640 mg, 0.25 mmol, 5 moi%) in l-bromoperfluorooctane (2.5 mL) and a solution ofcyclooctene (550 mg, 5 mmol) and isobutyraldehyde (720 mg, 10 mmol) in toluene The biphasic system was warmed to SO "C affording a single phase and was stirred at that temperature for 5 h under an oxygen atmosphere (oxygen balloon). The reaction mixture was cooled to O T , and the phases separated. The brown perfluorinated phase containlng the catalyst was separated and can be reused for further experiments. The organic phase was washed with 2Maqueous NaOH in order to remove the acid formed as by-product. The toluene was evaporated and the product was purified by flash chromatography on silica gel (eluent: hexanesjfBuOMe 10: 1) yielding cyclooctene oxide (11 a) (517 mg, 4.1 mmol, 82%).

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“…Although the equilibrium constants for these disproportionation reactions are small (e.g., 10 -8 for a ca. 0.5V separation between E ~ values of radical ion and doubly charged ion half-reaction), the dianions and dications are usually very reactive species; this disproportionation decay of radical ions, in connection with much faster reactions, however, has been discussed extensively (15)(16)(17). A useful estimate of the maximum rate of buildup of side-product (or rate of loss of reactant) can be derived as follows: Assuming that the electrolysis of the reacting component (e.g., A) is diffusion controlled, the moles of species A electrolyzed per pulse is moles electrolyzed per pulse ----idt/F -~ 2AC (Dtf/~)'/2 [5] where C and D are the concentration and diffusion coefficient of A, tf is the pulse length, and A the electrode area.…”

Section: Resultsmentioning

confidence: 99%

Electrogenerated Chemiluminescence: XXIII . On the Operation and Lifetime of ECL Devices

Laser

Bard²

1975

J. Electrochem. Soc.

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Factors affecting the lifetime of ECL devices, including decomposition of starting materials, formation of side products which react with radical ions or quench excited states, and filming of the electrodes are discussed. The mode of operation of the ECL device is shown to be important in determining its behavior and lifetime; operation of. (i) three-electrode pulsed potentiostatic, (ii) two-electrode pulsed voltage, (iii) two-electrode pulsed constant current, and (iv) thin-layer cells is discussed and illustrated, in studies of the Ru(bip)8 ~+ system in acetonitrile and the rubrene system in benzonitrile. Experimental Purification of the solvents, acetonitrile (ACN) and benzonitrile (BZN), the supporting e.~ectrolyte, tetran-butylammonium perchlorate (TBAP), and the reactants followed previous practice (7, 11). All experiments were conducted in a Vacuum Atmospheres (Los Angeles, California) Glove Box equipped with a Model MO 40-1 Dri-Train.

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Ion radicals. XVIII. Reactions of thianthrenium perchlorate and thianthrenium trichlorodiiodide

Cited by 121 publications

References 5 publications

Intermediacy of a Persistent Urazole Radical and an Electrophilic Diazenium Species in the Acid-Catalyzed Reaction of MeTAD with Anisole

Intermediacy of a Persistent Urazole Radical and an Electrophilic Diazenium Species in the Acid-Catalyzed Reaction of MeTAD with Anisole

Inter‐Ring Interactions in Dimers of Magnesium π‐Cation Radicals: Control by Solvent Polarity

Electrogenerated Chemiluminescence: XXIII . On the Operation and Lifetime of ECL Devices

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