Aromatic amines perchlorates

Spallino [32] has obtained aniline, p-nitraniline, m- and p-phenylenediamine perchlorates, by treating the corresponding amine sulphates with barium perchlorate 

The properties of aromatic amines perchlorates (T. Urbanski and Kowalski [34]) 

Perchlorate of Mel- ting point °C TempcratuA of initiation-explosion within 1 sec at °C Sensitiveness to shock — 10% of explosions from work of kg Lead block expansion cm3 Rate of detonation (glass tube 12 mm dia., density 1.1 g/cm3) m/sec 

Urbanski and Kowalski [34] examined the properties of those perchlorates as well as a range of others, not previously described, to determine their sensitiveness, stability, and explosive strength (Table 115). 

Only nitraniline perchlorates are fusible. The others explode without melting. 

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The broad absorptions of CPs characteristic of charge carriers such as bipolarons tail off in the IR, near ca. 6 /im, and subsequently, broad band variations in electro-chromic signature are then absent in most cases for conventional dopants. This can be seen fi om Fig. 3-15. showing Specular Reflectance for a poly(aromatic amine)/perchlorate here the "tails" of the bipolaron bands from the far-Visible and near-IR and the substantial dynamic range therein are clearly visible to ca. 6 fim. Beyond 6 / m, however, there is a nearly featureless absorption, and very little broad band variation in dynamic range. This tailing of the bipolaron absorptions well in to the IR is a characteristic feature of most CPs. 

The diazotization of amino derivatives of six-membered heteroaromatic ring systems, particularly that of aminopyridines and aminopyridine oxides, was studied in detail by Kalatzis and coworkers. Diazotization of 3-aminopyridine and its derivatives is similar to that of aromatic amines because of the formation of rather stable diazonium ions. 2- and 4-aminopyridines were considered to resist diazotization or to form mainly the corresponding hydroxy compounds. However, Kalatzis (1967 a) showed that true diazotization of these compounds proceeds in a similar way to that of the aromatic amines in 0,5-4.0 m hydrochloric, sulfuric, or perchloric acid, by mixing the solutions with aqueous sodium nitrite at 0 °C. However, the rapidly formed diazonium ion is hydrolyzed very easily within a few minutes (hydroxy-de-diazonia-tion). The diazonium ion must be used immediately after formation, e. g., for a diazo coupling reaction, or must be stabilized as the diazoate by prompt neutralization (after 45 s) to pH 10-11 with sodium hydroxide-borax buffer. All isomeric aminopyridine-1-oxides can be diazotized in the usual way (Kalatzis and Mastrokalos, 1977). The diazotization of 5-aminopyrimidines results in a complex ring opening and conversion into other heterocyclic systems (see Nemeryuk et al., 1985). 

The rate-determining step in the diazotization of aniline in aqueous perchloric acid below concentrations of 0.05 m (pH >0.7) is the formation of N203. The following A-nitrosation step is faster (rate equation of Scheme 3-12). However, with aromatic amines that are weaker nucleophiles than aniline, e.g. 4-nitroaniline, nitrosation is slower than the formation of N203, and the rate is second-order with respect to nitrous acid and first-order in amine (Scheme 3-13, Larkworthy, 1959). 

Hydrogen peroxide Organic compounds (reference 2) Nitric acid Aromatic amines Nitrosyl perchlorate Organic materials Ozone Aromatic compounds Perchloric acid Aniline, etc. 

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). 

Dwivedi, B. K. et al., Indian J. Chem., 1987, 26A, 618-620 Twelve tris-complexes [Sn(C104)2.3L] between tin(II) perchlorate and Schifif bases derived from salicylaldehyde, anisaldehyde, or 2-hydroxy-l-naphthaldehyde and aromatic amines were investigated for thermal instability. 

El-Kommos and Emara [47] determined primaquine and other secondary aromatic amines pharmaceuticals by a spectrophotometric method using 4-dimethyl amino cinnamaldehyde. The reaction of the reagent with primaquine and with the other amines was investigated. Powdered tablets were extracted with methanolic 0.1 M perchloric acid. The extract was mixed 1 1 with methanolic 0.2% of 4-dimethyl amino cinnamaldehyde and the mixture was diluted with methanol before measurement of the absorbance at 670 nm for primaquine phosphate. Beer s law was obeyed for 2-20 pg/mL of primaquine. The pink and green color formed with primaquine was stable for at least 24 h. Recoveries were good. Amodiaquine did not interfere with the determination of primaquine. 

The lithium perchlorate-catalysed aminolysis of styrene oxide has been investigated. Amines of low nucleophilicity, such as aromatic amines, give almost exclusively products of type 30, sterically hindered amines (diisopropylamine, dicyclohexylamine etc.) give... 

Alkali, alkaline-earth, and rare-earth metal cations also catalyze electron transfer reactions. Thus, in the pair of Co -tetraphenylporphyrin complex with BQ, no redox reaction takes place, or it takes place too slowly to be determined. The metal cations promote this reaction. For example, in the presence of 80(0104)3, the corresponding rate constant of 2.7 X 10 M s was observed. BQ transforms into benzosemiquinone under these conditions (Fukuzumi and Ohkubo 2000). Zinc perchlorate accelerates the reaction between aromatic amines and quinones (Strizhakova et al. 1985). This reaction results in the formation of charge-transfer complexes [ArNHj Q ]. The complexes dissociate in polar solvents, giving ion-radicals ... 

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. 

It has been found possible (K. A. Hofmann and Zedtwitz [5]) to obtain the esters of perchloric acid by treating alcohols with nitrosyl perchlorate, N0C104-H20. Nitrosyl perchlorate is a stable, crystalline substance that reacts explosively on contact with aromatic amines. In the presence of alcohol the perchlorate and alkyl nitrite are produced. 

T. Urbanski and Kowalski [34] have studied the explosive properties of pyridine perchlorate as well as quinoline and its nitro derivative perchlorates. Due to the introduction of a nitro group the sensitiveness to shock of the quinoline perchlorate increased, but to a smaller extent than the authors had previously observed with primary aromatic amines. The introduced nitro group markedly favoured the increase of explosive strength of the perchlorates (Table 116). 

Zinc perchlorate accelerates the reaction between aromatic amine and quinones (Strizhakova et al. 1985). The reaction results in the formation of charge-transfer com-... 

Acid eluents serve a dual function. First, the acid will protonate the amine so that the amine will interact with the resin and the hydrogen ion will serve as the exchange ion in the chromatographic process. The eluent suitable for the separation of aromatic amines is an aqueous perchloric acid solution. Other mineral acids can also be used but may form complexes with metals in the sample or the chromatograph or oxidize components of the sample., ... 

Aminoalkyl and Related Acids. - Further development of the classical three component approach to aminoalkylphosphonates (the Kabachnik-Fields reaction) has been reported. The reaction of aldehydes, hydroxylamines and dimethyltrimethylsilyl phosphite using lithium perchlorate/diethyl ether as a catalyst gives N-trimethylsilyloxy-a-aminophosphonate derivatives. The catalytic activities of various lanthanide triflates as well as indium trichloride have been examined for the Kabachnik-Fields type reactions of aldehydes, amines and the phosphorus nucleophiles HP(0)(0Et)2 and P(OEt)3 in ionic liquids. TaCb-Si02 has been utilized as an efficient Lewis acid catalyst for the coupling of carbonyl compounds, aromatic amines and diethyl phosphite to produce a-... 

When 131 is treated with primary aromatic amines and perchloric acid in ethanol, salts 132 are obtained. 

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