Potassium permanganate system

The amination of quinazoline (241) with sodium amide in DMA has been described to give 4-aminoquinazoIine (242) in 40% yield (60YZ245). In the potassium amide/liquid ammonia/potassium permanganate system of van der Plas, quinazoline gave 62% 242 and 2% 4,4 -diquinazolylamine (243) (Scheme 80) (82JHC1285). 

Xue, Y., He, Y, and Lu, J. Chemiluminescence reaction of imipramine-glyoxal-potassium permanganate system. Penxi Shiyanshi 18(3) 49-51, 1999. 

Liquid ammonia and potassium permanganate system were also effectively applied to introduce an imino group in the highly electron-deficient A-alkylazinium salts [30, 39]. 

Phenol can be oxidi2ed and hence removed, ie, to levels <20 / g/L, from wastewater (248). Moreover, addition of potassium permanganate to the return activated sludge results in reduction of odors issued from the aeration tanks of conventional activated sludge wastewater treatment plants without any change occurring to the microbiology of the system (249). 

Manufacture. The only current U.S. manufacturer of trimesic acid is Amoco Chemical Co. It is produced by oxidation of mesitylene (1,3,5-trimethylbenzene) via the Hquid-phase oxidation in acetic acid using the cobalt— manganese—bromine catalyst system (138). This is a variant of the system used to produce terephthaUc and isophthaUc acids as well as trimellitic anhydride. American Bio-Synthetics Corp. did produce it by batch oxidation of mesitylene with potassium permanganate. 

The reaction mixture is filtered. The soHds containing K MnO are leached, filtered, and the filtrate composition adjusted for electrolysis. The soHds are gangue. The Cams Chemical Co. electrolyzes a solution containing 120—150 g/L KOH and 50—60 g/L K MnO. The cells are bipolar (68). The anode side is monel and the cathode mild steel. The cathode consists of small protmsions from the bipolar unit. The base of the cathode is coated with a corrosion-resistant plastic such that the ratio of active cathode area to anode area is about 1 to 140. Cells operate at 1.2—1.4 kA. Anode and cathode current densities are about 85—100 A/m and 13—15 kA/m, respectively. The small cathode areas and large anode areas are used to minimize the reduction of permanganate at the cathode (69). Potassium permanganate is continuously crystallized from cell Hquors. The caustic mother Hquors are evaporated and returned to the cell feed preparation system. 

Tliis methodology has also been extended to the use of liquid methylamine/ potassium permanganate (LMA/PP system). When this system is applied to a number of 3-nitro-l,8-naphthyridines (92a-92g), the C-4 position could be successfully substituted by methylamino group yielding 93a-93f. Tire intermediary 4-methylamino-[Pg.305]

This is known as the Prout—Tompkins equation and has found application to many systems, in addition to the thermal decomposition of potassium permanganate [465] with which it is often associated. The kinetic behaviour of silver permanganate was somewhat different and in a variation of... 

When it is mixed with small quantities of sulphuric acid and in the presence of water traces, it is thought to form permanganic acid, HMn04, which is very unstable and a violent oxidant. Thus, this system incandesces in the presence of ammonia. Mixtures of potassium permanganate /peroxomonosulphuric acid have also been used to measure sulphur in the presence of carbon. However, this is not recommended since it is highly likely to detonate. 

Cyanide and thiocyanate anions in aqueous solution can be determined as cyanogen bromide after reaction with bromine [686]. The thiocyanate anion can be quantitatively determined in the presence of cyanide by adding an excess of formaldehyde solution to the sample, which converts the cyanide ion to the unreactive cyanohydrin. The detection limits for the cyanide and thiocyanate anions were less than 0.01 ppm with an electron-capture detector. Iodine in acid solution reacts with acetone to form monoiodoacetone, which can be detected at high sensitivity with an electron-capture detector [687]. The reaction is specific for iodine, iodide being determined after oxidation with iodate. The nitrate anion can be determined in aqueous solution after conversion to nitrobenzene by reaction with benzene in the presence of sulfuric acid [688,689]. The detection limit for the nitrate anion was less than 0.1 ppm. The nitrite anion can be determined after oxidation to nitrate with potassium permanganate. Nitrite can be determined directly by alkylation with an alkaline solution of pentafluorobenzyl bromide [690]. The yield of derivative was about 80t.with a detection limit of 0.46 ng in 0.1 ml of aqueous sample. Pentafluorobenzyl p-toluenesulfonate has been used to derivatize carboxylate and phenolate anions and to simultaneously derivatize bromide, iodide, cyanide, thiocyanate, nitrite, nitrate and sulfide in a two-phase system using tetrapentylammonium cWoride as a phase transfer catalyst [691]. Detection limits wer Hi the ppm range. 

The effect of inorganic additives upon ignition delay in anilinium nitrate-red finning nitric acid systems was examined. The insoluble compounds copper(I) chloride, potassium permanganate, sodium pentacyanonitrosylferrate and vanadium(V) oxide were moderately effective promoters, while the soluble ammonium or sodium metavanadates were very effective, producing vigorous ignition. 

Such carbonyls may be further oxidized using potassium permanganate (KMnO and perchloric acid (HCIO4) to convert all of these groups into carboxylic acids. Once functionalized in this manner, the nanotubes can be fully dispersed in aqueous systems. Kordas et al. (2006) used these derivatives to print nanotube patterns on paper or polymer surfaces to create conductive patterns for potential use in electronic circuitry. The carboxylates also may be used as conjugation sites to link other ligands or proteins to the nanotube surface using a carbodiimide reaction as previously discussed (Section 1, this chapter Chapter 2, Section 1.11 Chapter 3, Section 1). 

The naphthalene-like, aromatic stmcture of 1,2,3-benzothiadiazole imparts stability to the system that survives exposure to 20% potassium hydroxide at 150°C or 27% sulfuric acid at 200 °C. It is not oxidized by potassium permanganate, potassium ferricyanide, chromic acid, or dilute nitric acid <1996CHEC-II(4)289>. Electrophilic substitution occurs in the benzo ring, predominantly at the 4-position. Chlorine in the 6-position is displaced by a variety of nucleophiles <1975SST670>. 

Oxidation at the benzylic position of indane -with potassium permanganate (Eq. 3.30) gives indanone in good yields and no PTC is necessary [133]. In a two-phase system consisting of an aqueous solution of KMn04 and indane in benzene an 80 % yield can be obtained under a reduced pressure of ca. 450 Torr. The authors explain this effect by the size of the cavitation bubbles, which is dictated to some extent by the over pressure. An optimal energy transformation, from acoustic to chemical, can thus take place. 

The Sir Galahad has been used in many locations around the world. For example, Cameron et al. [11] have used the instrument to vahdate plant operations in Thailand. In this apphcation the Sir Galahad was compared initially with other systems. Acidic vapour was found to cause false positive results in the other systems, whereas the Sir Galahad provided consistently rehahle data. Tests have recently been carried out to compare the Sir Galahad with conventional techniques—Table 3.1 shows results produced using the Sir Galahad and the ISO 6978 potassium permanganate absorption method. 

Oxidation of methylpyridines in 60-80 % sulphuric acid at a lead dioxide anode leads to the pyridinecarboxylic acid [213]. The sulphuric acid concentration is critical and little of the product is formed in dilute sulphuric acid [214]. In these reactions, electron loss from the n-system is driven by concerted cleavage of a carbon-hydrogen bond in the methyl substituent. This leaves a pyridylmethyl radical, which is then further oxidised to the acid, fhe procedure is run on a technical scale in a divided cell to give the pyridinecarboxylic acid in 80 % yields [215]. Oxida-tionof quinoline under the same conditions leads to pyridine-2,3-dicarboxylic acid [214, 216]. 3-HaIoquino ines afford the 5-halopyridine-2,3-dicarboxylic acid [217]. Quinoxaline is converted to pyrazine-2,3-dicarboxylic acid by oxidation at a copper anode in aqueous sodium hydroxide containing potassium permanganate [218]. 

Several TLC methods have been described for the identification of isoxsuprine [36]. In all systems, silica gel G, dipped in sodium hydroxide solution or methanol, was used as the stationary phase. Either 100 1.5 methanol strong ammonia, 75 15 10 cyclohexane toluene diethylamine, or 90 10 chloroform methanol was successfully used as the mobile phase. In all systems, the spray reagent used to develop the places was acidified potassium permanganate solution. 

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