Tetraethylammonium -toluenesulfonate

The same homoporphyrin, i.e., 4.57, could also be prepared directly from dideoxybiladiene-ac dihydrobromide 4.55 via anodic oxidation at 800 mV vs. Ag/ AgCl in DMF using tetraethylammonium toluenesulfonate as the supporting electro-lyte. In a similar fashion, dideoxybiladiene-ac dihydrobromide 4.58 could be cyclized via anodic oxidation to generate the metal-free homoporphyrin derivative 4.59 (no exo/endo stereochemistry was specified for this compound) (Scheme 4.1.21). 

Amino acids may also be prepared from azomethine compounds by reducing them in the presence of carbon dioxide [34—38]. Thus reduction of benzylidene aniline (IV) in molten tetraethylammonium -toluenesulfonate saturated with carbon dioxide at 140°C gave V-phenyl-phenylglycine (60% yield) [34], [Eq. (9)]. In DMF a similar yield was obtained together with small amounts of a dimer and some phenylbenzylamine [38]. 

Table 5. Dissociation constants (—log Kg = pKo) of 1 1 complexes of anionic guests with host 24 in water at 298 K (supporting electrolyte 0.1 M sodium- or tetraethylammonium toluenesulfonate, methods A = pot itiometry, B = pH titraticm, C = photometry)" ...

PPy-p-toluenesulfonic acid monohydrate 9. PPy-tetraethylammonium toluenesulfonate 10. Ployanihne-NaHSO 11. Poly(3-methylthiophene-tetraethylammonium tetralluoroborate) methacrylate) 7. Poly(styrene-co-butadiene) 8. Poly(vinyl stearate) 9. Hydroxypropyl ceUulose to. Poly(butadiene) 11. Poly (vinyl butyral)-co-vinyl alcohol-co-vinyl acetate 12. Ethyl ceUulose 13. Poly(vinyl acetate) 14. Poly(4-vinyl pyridine) dibenzotetraazaannulene... 

PP polypyrrole, PPP/ -polyphenylene, AcCA acetonitrile, C104 LiClO, TCNQ 7,7,8,8-tetracyanoquinodimethane, TOS tetraethylammonium / -toluenesulfonate Source Reprinted with permission from Blackwood and Josowicz (1991). Copyright 1991 American Chemical Society... 

Some typical results are shown in Table 2. The table shows that oxidation of conjugated dienes such as isoprene, piperylene (1,3-pentadiene), cyclopentadiene and 1,3-cyclohexadiene with a carbon anode in methanol or in acetic acid containing tetraethylammonium p-toluenesulfonate (EtjNOTs) as the supporting electrolyte yields mainly 1,4-addition products2. 1,3-Cyclooctadiene yields a considerable amount of the allylically substituted product. 

Electrolysis of b-al Ionic ketone 61 at a controlled cathode potential of-2.43 V (versus Ag/AgI) in anhydrous DMF using tetraethylammonium p-toluenesulfonate as co-electrolyte provides the derived ketyl radical that undergoes a 5-exo-trig selective ring closure, presumably via transition structure 62 (Scheme 11.19). The cyclization product is further reduced and subsequently protonated to afford traus-configurcd cyclopentanol 63 as single diastereomer in a total yield of 55% [80]. 

O6F12RUC12H2, Ruthenium, dicarbonylbis(hexa-fluoroacetylacetonato)-, 34 115 O6NVC14H20, Vanadate(l-), hexacarbonyl-, tetraethylammonium, 34 98 O7AIN2SC41H61, Aluminum, dimethanol-1,2-bis(2-hydroxy-3,5-bis(tert-butyl)benzylide-neimino)ethane-, para-toluenesulfonate, 34 18... 

The oxidation of enol acetates in acetic acid containing tetraethylammonium p-toluenesulfonate gives four types of compounds (equation 23) conjugated enones (A), a-acetoxycarbonyl compounds (B), geminal diacetoxy compounds (C) and triacetoxy compounds (D). Similar to enol ethers, the Erst reactive intermediates are cation radicals generated from enol acetates by one-electron oxidation. The yields and the distribution of products A, B, C and D depend on the structure of the starting enol acetates and the reaction conditions. ... 

The anodic oxidation of 1,2-diols and their ether derivatives is a simple and clean method for the fission of glycols to the corresponding carbonyl compounds (equation 1). The reaction is carried out using carbon electrodes in methanol containing tetraethylammonium p-toluenesulfonate as a supporting electrolyte. ... 

Thiazole A -oxides can easily be alkylated on the oxygen. For example, Ar-(alkoxy)-5-(p-methoxyphenyl)-4-methylthiazole-2(377)-thiones were prepared from Ar-(hydroxy)-5-( -methoxyphenyl)-4-methylthiazole-2(3//)-thione tetraethylammonium salt and an appropriate alkyl chloride or tosylate in moderate to good yields <20060BC2313>. A -Methoxythiazole-2(377)-thiones were synthesized from the A -hydroxythiazole-2(3//)-thiones by treatment first with a tetraalkylammonium hydroxide in methanol and then methyl ra-toluenesulfonate in DMF <2005EJ0869>. 

Although the electrochemical coupling to form ADN had been known since the 1940s, the breakthrough came only when Baizer found out that the use of quaternary ammonium salts such as tetraethylammonium /7-toluenesulfonate as supporting electrolytes led to mass yields of 90% of ADN [75]. Following Baizer s discovery, an intensive process development effort was undertaken at Monsanto s Technical Centre in Pensacola, Florida [76]. 

Reaction of l-chloro-4,4-bis(chloromethyl)pentane with magnesium in diethyl ether, followed by quenching with carbon dioxide, gave 4-(l-methylcyclopropyl)butanoic acid in 68% yield. Cyclopropane derivatives with electron-withdrawing substituents 5 were prepared by elec-troreductive dechlorination of 2,4-dichlorobutanoic acid derivatives in dimethyl sulfoxide solution in the presence of tetraethylammonium 4-toluenesulfonate at ambient temperature (yields 51 -90%).The starting materials for compounds 5 can easily be obtained by copper (I)-catalyzed photochemical addition of dichloromethane to electron-deficient alkenes. Electrochemical reductive 1,3-debromination has also been achieved however, it is of little synthetic value (experimental details are described in ref 16, with yields ranging from 39 to 94%). meso- and dimethyl sulfoxide gave equal amounts of cis- and transA, 2-dimethylpropane. ... 

The 8-phenylsulfonyl derivative 86 was obtained when a solution of perhydropyrido[l,2-c][l,3]oxazin-l-one (85) and tetraethylammonium p-toluenesulfonate was electrolyzed and the evaporated residue was treated with benzenesulfinic acid and anhydrous calcium chloride (91T1311). From the 8-phenylsulfonyl derivative (86), the 7,8-unsaturated derivative (87) and different 8-substituted derivatives (88-90) could be prepared stereose-lectively (90SL48, 90SL749 91T1311) (see Scheme 13). 

The key to this process [63, 64] was the addition of a quaternary ammonium salt (tetraethy-lammonium p-toluenesulfonate or tetraethylammonium ethylsulphate) to the reaction medium, which increased the solubility of acrylonitrile in the aqueous electrolyte and generated an aprotic organic layer on the cathode surface that inhibited the synthesis of propionitrile by-products (formed by the simple reduction of acrylonitrile). 

Careful selection of the supporting electrolyte is a key point in the hydrodimerization process. Monsanto has chosen tetraethylammonium p-toluenesulfonate for their solution process. In concentrations of from 20% to 40%, it increases the solubility of acrylonitrile in the anolyte and retards the formation of byproduct. Asahi Chemical uses less hydrophobic supporting electrolyte, in concentrations of about 10%, for their emulsion process. Thus, adiponitrile formed in the emulsion process is separated from the reaction mixture by physically breaking down the emulsion and then separating the oil layer. The loss of supporting electrolyte and the electric power consumption are lower in the emulsion process than in the solution process. 

Sun et al. [82] reported the synthesis of polypyrrole films with conductivities greater than 500 S cm". Films were prepared from pyrrole monomer in propylene carbonate containing tetraethylammonium /7-toluenesulfonate as the electrolyte. These films were also shown to be anisotropic. Temperature, electrode dimensions, current density, and solvent type were observed to effect the conductivity of the polymer. A sample prepared at -20 C with a current density of 3.0 mA/cm on a 2 X 5 cm titanium substrate had a conductivity of 514 S cm". A film deposited on a long narrow substrate had an unusually high conductivity of 996 S cm". BASF has developed a pinhole-free freestanding polypyrrole film by electrochemical synthesis with benzosulfonic acid as dopant [83,84]. 

The electrochemical polymerization of azulene produced thick films with conductivities ranging from 10" to 1 S cm" [374]. A platinum anode was immersed in a solution of 10" M azulene (Fig. 24) and 0.1 M tetraethylammonium tetrafluo-roborate, perchlorate, hexafluorophosphate, or p-toluenesulfonate in acetonitrile. 

OioNiH2oS4W3, Tungsten, decaaquatetrasullido-nickel-tri-, ion in solution, 33 161 O12C0S2C14H26, Cobalt(ll), hexaaqua-, bis(p-toluenesulfonate), 33 100 O12CU5N6C60H64 DMF, Cuprate(ll), tetrakis-(naphthoylhydroximato)penta-, bis-[tetraethylammonium(l+)] dimethylfor-mamide, 33 72... 

Tetracyanoethylene, CTC formation, 183, 184 Tetracyanoethylene oxide, olefin adducts, 227 Tetracyclone 5CC tetraphenylcyclopentadienone, 113 Tetradecene, MA copolymerization, 586 Tetraethylammonium p-toluenesulfonate, 259 Tetrahydrofuran... 

The principle has been known since the 1940s, but it was M.M. Baizer who initiated in 1959 the use of quaternary ammonium salts such as tetraethylammo-nium p-toluenesulfonate in this reaction, leading to mass yields of 90% ADN. Together with Monsanto he commercialized and improved the process ever since. First used process setups consisted of divided cell reactors with catholytes of an aqueous solution of ACN and ADN in 40% tetraethylammonium ethyl sulfate, an anolyte of diluted sulfuric acid, separated... 

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