Tetraethylammonium perchlorate

FIGURE 2-11 Spectra for a series of applied potentials (mV vs. Ag/AgCl) during thin-layer spectroelectrochemical experiment on 1.04 x 10 3 M [Tc(III)(dmpe)2Br2]+. Medium is dimethylformamide containing 0.5 M TEAP = tetraethylammonium perchlorate. (Reproduced with permission from reference 27.)... 

Fig. 1. i-E curve for the reduction of anthracene at a dropping mercury electrode in acetonitrile containing 01m tetraethylammonium perchlorate. 

Tetraazido benzene quinone Tetraethylammonium perchlorate (dry) Tetramethylene diperoxide dicarbamide Tetranitro diglycerin... 

In pioneering studies [47], the SECM feedback mode was used to study the ET reaction between ferrocene (Fc), in nitrobenzene (NB), and the aqueous mediator, FcCOO, electrochemically generated at the UME by oxidation of the ferrocenemonocar-boxylate ion, FcCOO. Tetraethylammonium perchlorate (TEAP) was applied in both phases as the partitioning electrolyte. The results of this study indicated that the reaction at the ITIES was limited by the ET process, provided that there was a sufficiently high concentration of TEAP in both phases. 

Figure 2.106 OTTLE cell cyclic voltammogram of 0.01 M 1,4-benzoquinone in dimethyl-suiphoxide solution containing 0.5M tetraethylammonium perchlorate. Scan rate 0.5mVs. ...

Figure 2.107 (a) UV-visible absorption spectra of 5 x 10 3 M 1,4-benzoquinone (BQ), its radical anion (BQ ) and dianion BQ2 ) in dimethylsulphoxide solution containing 0,5 M tetra-ethylammonium perchlorate, (b) FTIR absorbance difference spectra of 0.02 M 1,4-benzoquinone in dimethylsulphoxide solution containing 0.5 M tetraethylammonium perchlorate. Positive absorbances are due to the 1,4-benzoquinone radical anion (BQ ) and dianion (BQ2 ) recorded at -1.00 V and -1.80 V respectively. Negative absorbances are due to 1,4-benzoquinone (BQ) present at the reference potential +0.1 V. From Ranjith et ai (1990). 

The electrochemical cyclization of bis(aminomethylenemalonates) (1394) in acetonitrile containing 5% water and tetraethylammonium perchlorate afforded tetrahydroquinoxalines (1395) in 90-96% yields (81ZC286). 

Table 11 Anodic oxidation of ST-Bu4NNu in acetonitrile with tetraethylammonium perchlorate as supporting electrolyte."...

Poly(dimercuryimmonium perchlorate), 4012 Pyridinium perchlorate, 1863 Tetraethylammonium perchlorate, 3088 Tetrafluoroammonium perchlorate, 3986 N. N. N. A-Tctramcthv 1 formam idinium perchlorate, 2026 Triaminoguanidinium perchlorate, 0515 Trimethylammonium perchlorate, 1322 Trimethylhydroxylammonium perchlorate, 1323 Tri(4-tolyl)ammonium perchlorate, 3824 Uronium perchlorate, 0491... 

Data from Ref. 137, measured at 2 mM in CH3CN with 100 mM tetraethylammonium perchlorate, with a platinum or glassy carbon rotating disk electrode and a scan speed of 250 mV s. ... 

The one-electron reduction of 3,4,5-trimethoxyphenyl glyoxal with potassium tert-butoxide in DMSO gives rise mainly to the ctT-semidione, whereas on electrolysis in dimethylformamide, in the presence of tetraethylammonium perchlorate as the carrier electrolyte, the main product is the trans isomer (Sundaresan and Wallwork 1972 Scheme 3.47). 

The electrochemical rate constants of the Zn(II)/Zn(Hg) system obtained in propylene carbonate (PC), acetonitrile (AN), and HMPA with different concentrations of tetraethylammonium perchlorate (TEAP) decreased with increasing concentration of the electrolyte and were always lower in AN than in PC solution [72]. The mechanism of Zn(II) electroreduction was proposed in PC and AN the electroreduction process proceeds in one step. In HMPA, the Zn(II) electroreduction on the mercury electrode is very slow and proceeds according to the mechanism in which a chemical reaction was followed by charge transfer in two steps (CEE). The linear dependence of logarithm of heterogeneous standard rate constant on solvent DN was observed only for values corrected for the double-layer effect. 

For the rapid electron transfer process, which follows a reversible chemical step (CE), a procedure is presented for the determination of chemical and electrochemical kinetic parameters. It is based on convolution electrochemistry and was applied for cyclic voltammetry with digital simulation [59] and chronoamperometric curves [60]. The analysis was applied to both simulated and experimental data. As an experimental example, the electroreduction of Cd(II) on HMDE electrode in dimethylsulphoxide (DM SO) [59] and DMF [60] with 0.5 M tetraethylammonium perchlorate (TEAP) was investigated. 

The S values applicable in acetonitrile, as determined by Pavlishchuk and Addison, are as follows (TEAP = tetraethylammonium perchlorate) ... 

Indium metal (0.5 g) is maintained at +50 V in a solution phase of 100 mL of benzene-methanol (3 1, v/v) containing 10 mg of tetraethylammonium perchlorate. Benzene is dried with sodium-naphthaquinone and is distilled before use (all under nitrogen) methanol is analytical grade reagent. The cell must be cooled in an ice bath throughout the experiment, since appreciable amounts of heat are evolved. 

Indium metal (0.8 g) is maintained at +50 V in a solution phase of 80 mL of 2,4-pentanedione and 5 mL of methanol containing 50 mg tetraethylammonium perchlorate. Under these conditions, a current of 100 mA is recorded. Electrolysis is continued for 2 hours at room temperature the metal is almost completely consumed in this period. The final solution is pale yellow, suggesting some decomposition of the diketone. 

Tetraethylammonium perchlorate [2567-83-1] M 229.7. Crystd repeatedly from water, aqueous MeOH, acetonitrile or acetone, and dried at 70° under vacuum for 24h. [Cox et al. JACS 106 5965 1984, Liu et al. JACS 108 1740 1986 White and Murray JACS 109 2576 1987]. Also twice crystd from ethyl acetate/95% EtOH (2 1) [Lexa et al. JACS 109 6464 1987],... 

Benzothiazolium salts in aqueous solution with tetraethylammonium perchlorate as supporting electrolyte are reduced in two one-electron steps.270 The first produces a radical that dimerizes with a radical-substrate reaction as the rate-determining step. The product is dimerized in the 2-position. Reduction at the potential of the second step produces the 2,3-dihydrobenzo-thiazole. 

An interesting compound (205), isolated in ca. 15% yield, is obtained from the electrochemical oxidation of indole in acetonitrile using tetraethylammonium perchlorate as an electrolyte (78MI30503). Although it is obvious that the 3-substituent arises from the tetraethylammonium ion, no mechanism for the reaction is immediately apparent. 

A different route to pyrones is the preparative electrochemical oxidation of enamines in acetonitrile in the presence of tetraethylammonium perchlorate (88MI2) (Scheme 46). The synthesis of 2-pyrone derivatives has been carried out by reaction of /3-dicarbonyl compounds with methyl-a-benzoylamino-/3-dimethylaminoacrylate (96JHC751). Thiapyran derivatives can be obtained by interaction of enamines based on (/3-amino-a-cyanoacryloylmethyl)pyridinium chloride derivatives with carbon disulfide (95M711).The synthesis of pyridine derivatives based on analogous enamines has been described as well (95M711). 

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