Toluidine perchlorates

Fig. 4.7 shows the titration with perchloric acid of a mixture of piperidine, ethylenediamine and p-toluidine. Fig. 4.8 illustrates the effect of different chain lengths on the titration (with perchloric acid) of diamines in nitrobenzene containing 2.5% (v/v) of methanol once the first amino group of EDA has been protonated, the resulting proton bridge with the lone pair of electrons of the second amino group lowers the basicity of the latter considerably the effect decreases on the introduction of more intermediate CH2 groups until complete disappearance when six are present. 

As the anhydride of nitrous and perchloric acids, it is a very powerful oxidant. Pinene explodes sharply acetone and ethanol ignite, then explode ether evolves gas, then explodes after a few s delay. Small amounts of primary aromatic amines-aniline, toluidines, xylidines, mesidine-ignite on contact, while larger amounts exploded dangerously, probably owing to rapid formation of diazonium perchlorates. Urea ignites on stirring with the perchlorate, (probably for a similar reason). 

Similarly, benzene and hydrazoic acid in the presence of a mixture of fluorosulphonic and trifluoromethanesulphonic acid give aniline quantitatively. From toluene 100% of a mixture of o-, m- and p-toluidines is obtained and bromobenzene yields 42% o-bromoaniline and 47% p-bromoaniline, Butyl azide gives iV-butylarylamines under these conditions89. Photolysis of 1-aminoquinolinium perchlorate (76) in aromatic hydrocarbons (benzene, toluene, ethylbenzene or mesitylene) in the presence of 18-crown-6 affords arylamines, e.g. aniline and p-toluidine, by way of the nitrenium ion90 cf Reference 91. 

Perchlorate, CHj.Cg. . CK jndls extremely sensitive to shock, can be exploded by touching even when wet with ether v si sol in w was prepd by diazotizing o-toluidine-hydrochloride with NaN02 in the presence of perchloric acid... 

Dimethyl-2,4-diphenyl-3-azapyrylium perchlorate 381 is converted under the Vilsmeier-Haack reaction conditions into the N,jV-dimethylaminovinyl derivative 382. By refluxing 382 in acetic acid mixed with either ammonium acetate or / -toluidine, compound 383 was obtained by an unusual recyclization via elimination of the iV,A-dimethylaminovinyl group (equation 109). 

METHYL-o-TOLUIDINE (95-68-1) Combustible liquid (flash point 205°F/96°C). Violent reaction with strong oxidizers, strong acids, nitrosyl perchlorate. Mixtures with hypochlorites form sensitive explosive chloroamines. Incompatible with aldehydes, non oxidizing mineral acids, cellulose nitrate (of high surface area), cresols, isocyanates, nitrates, nitric acid, organic anhydrides, phenols, sulfuric acid. 

One of the other attractions of polyaniline is the ease of preparing (or even commercial availability) of substituted derivatives. The simplest example is the methyl derivative poly(o-toluidine), for which the EQCM in conjunction with PBD has been used to obtain the individual anion, cation, and solvent fluxes/film populations. By comparing the EQCM frequency responses to a potential sweep [46] and a potential step [154], it is possible to show that the competing ion transfers have intrinsic potential and timescale dependencies the contributions of the protons and perchlorate ions are also pH dependent. One interesting feature is that anion... 

Figure 4. Diazotisation of aniline (O), chloroaniline ( ) and -toluidine ( ) in concentrated perchloric acid.

CioHsCr03, 7T-(Tricarbonylchromium)toluene, 43B, 1095 CioHgCrNOg, Tricarbonylchromium-o-toluidine, 32B, 368 Cl 0H1 gAg4Cl j02o f Naphthalene-tetrakis(silver perchlorate) tetrahyd-rate, 40B, 549... 

Cl8H30CI2CU2N4O10 f a-Di-M hydroxo-bis(2-(2-dimethylaminoethyl)pyrid-ine)dicopperUl) perchlorate, 40B, 953 Cl8H30CI2CU2N4O10 f p-Di-M hydroxo-bis(2-(2-dimethylaminoethyl)pyrid-ine)dicopper(II) perchlorate, 40B, 954 Cl8H30CUN2O5, Aquobis(norephedrinato)copper(II) dihydrate, 44B, 998 Cl8H30CUN2O7, Diacetatocopper(II)-bis(p-toluidine) trihydrate, 37B, 600... 

Fig. 18. Polarization curves in 1 N perchloric acid solution with various concentrations of p-toluidine [91] 1) 0 2) 0.1 mole/liter 3) 0.15 mole/ liter 4) 0.2 mole/ liter 5) 0,2 mole/ liter, with variation of current density in reverse order (from large to small).

It is interesting that in acidic solutions of p-toluidine [91] and tribenzylamine [92] in the presence of iodide and perchlorate ions... 

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