With permanganate solutions

Trimethylacetic acid may be made by the hydrolysis of tert-butyl cyanide with weak hydrochloric acid at ioo0.1 It is also obtained by oxidation of trimethylpyroracemic acid with silver oxide or potassium dichromate and sulfuric acid,2 by oxidation of tertf-butylethylene with permanganate solution,3 or by oxidation of dimethyl 2,2-propanol with chromic acid.4 Schroeter reports the formation of trimethylacetic acid by rearrangement of the oxime of trimethylacetophenone to give the anilide of trimethylacetic acid, which can be hydrolyzed to give the acid.5... 

Discussion. Nitrites react in warm acid solution (ca 40 °C) with permanganate solution in accordance with the equation ... 

N.B.—Ether, which is kept in air and light, develops peroxides which are explosive and remain in the residue after distillation. These can usually be removed by shaking with permanganate solution or with silver nitrate and caustic potash solutions. Ether, therefore, should always be distilled from a water bath to avoid heating the residue to a high temperature. 

Extent of reaction can be ascertained by titrating the remaining oxalic acid with permanganate solution. For best results this... 

Finally, the oxalic acid is titrated with permanganate solution of accurately known concentration, based on the redox reaction... 

Hair Washing of samples with acetone and water digestion with HN03 and heat oxidation with permanganate solution and heat cooling and addition of hydroxylamine hydrochloride reduction of mercury with SnCI2 purging to detector CVAAS NR 100-101 Pineau et al. 1990... 

As well as the p-hydroxybenzoate esters, sorbic and benzoic acids are also often used in food technology as preservatives. According to Copitjs-Peereboom [20], these preservatives may be satisfactorily separated on cellulose layers (Firm 83) using n-butanol-35% ammonium hydroxide-water (70 + 20 + 10) at chamber saturation. Visualisation is performed with a bromophenol blue-methyl red solution (Rgt. No. 29), followed by spraying with permanganate solution. 

According to Vobecky et al. [88], the triphenyl derivatives of antimony, bismuth, phosphorus and arsenic and also ditolyl-teUurium isomers can be separated on alumina layers using petrol ether (hR/-values of the first two, 69 and 62 respectively). They may be visualised by spraying with permanganate solution. 

In what way does a solution of hydrogen peroxide react with (a) chlorine water, (b) potassium permanganate solution, (c) potassium dichromate solution, (d) hydrogen sulphide 50 cm of an aqueous solution of hydrogen peroxide were treated with an excess of potassium iodide and dilute sulphuric acid the liberated iodine was titrated with 0.1 M sodium thiosulphate solution and 20.0 cm were required. Calculate the concentration of the hydrogen peroxide solution in g 1" ... 

Peroxides can usually be completely removed from a sample of ether by thorough shaking with aqueous potassium permanganate solution. 

Traces of aldehyde are produced. If ether of a high degree of purity is required, it should l>e further shaken with 0-5 per cent, potassium permanganate solution (to convert the aldehyde into acid), then with i> per cent, sodium hydroxide solution, and finally with water. 

The analytical reagent grade is suitable for most purposes. The commercial substance may be purifled by shaking for 3 hours with three portions of potassium permanganate solution (5 g. per litre), twice for 6 hours with mercury, and Anally with a solution of mercuric sulphate (2-5 g. per litre). It is then dried over anhydrous calcium chloride, and fractionated from a water bath at 55-65°. The pure compound boils at 46-5°/760 mm. 

Chakactkrisation of Unsaturatkd Aliphatic Hydrocarbons Unlike the saturated hydrocarbons, unsaturated aliphatic hydrocarbons are soluble in concentrated sulphuric acid and exhibit characteristic reactions with dUute potassium permanganate solution and with bromine. Nevertheless, no satisfactory derivatives have yet been developed for these hydrocarbons, and their characterisation must therefore be based upon a determination of their physical properties (boiling point, density and refractive index). The physical properties of a number of selected unsaturated hydrocarbons are collected in Table 111,11. 

By oxidation of primary alcohols with alkaline potassium permanganate solution or with a dichromate and dilute sulphuric add, for example ... 

Oxidation of 10-undecynoic acid to sebacic acid. Dissolve 2 00 g. of the acid, m.p. 41-42°, in 50 ml. of water containing 0 -585 g. of pure anhydrous sodium carbonate. Saturate the solution with carbon dioxide and add O IN potassium permanganate solution (about 1500 ml.) slowly and with constant stirring until the pink colour remains for half an hour the addition occupies about 3 hours. Decolourise the solution with a httle sulphur dioxide and filter off the precipitated acid through a... 

Preparation of the sulphones. Dissolve the 2 4-dinitrophenyl-sulphide in the minimum volume of warm glacial acetic acid and add 3 per cent, potassium permanganate solution with shaking as fast as decolourisation occurs. Use a 50 per cent, excess of potassium permanganate if the sulphide tends to precipitate, add more acetic acid. Just decolourise the solution with sulphur dioxide (or with sodium bisulphite or alcohol) and add 2-3 volumes of crushed ice. Filter off the sulphone, dry, and recrystaUise from alcohol. 

Oxidation of side chains. The oxidation of halogenated toluenes and similar compounds and of compounds with side chains of the type —CHjCl and —CH OH proceeds comparatively smoothly with alkaline permanganate solution (for experimental details, see under AromcUic Hydrocarbons, Section IV.9,6 or under Aromatic Ethers, Section IV,106). The resulting acid may be identified by a m.p. determination and by other teats (see Section IV,175). 

Aromatic aldehydes react with the dimedone reagent (Section 111,70,2). All aromatic aldehydes (i) reduce ammoniacal silver nitrate solution and (ii) restore the colour of SchifiF s reagent many react with sodium bisulphite solution. They do not, in general, reduce Fehling s solution or Benedict s solution. Unlike aliphatic aldehydes, they usually undergo the Cannizzaro reaction (see Section IV,123) under the influence of sodium hydroxide solution. For full experimental details of the above tests, see under Ali-phalic Aldehydes, Section 111,70. They are easily oxidised by dilute alkaline permanganate solution at the ordinary temperature after removal of the manganese dioxide by sulphur dioxide or by sodium bisulphite, the acid can be obtained by acidification of the solution. 

It is essential to apply both tests, since some symmetrically substituted ethylenic compounds (e.g., ilbene C4H5CH=CHCjHj) react slowly under tbe conditions of the bromine test. With dilute permanganate solution the double bond is readily attacked, probably through the intermediate formation of a cis diol ... 

Potassium permanganate test. Dissolve 0 -2 g. or 0 -2 ml. of the substance in 2 ml. of water or in 2 ml. of acetone (which gives a negative test with the reagent), and add 2 per cent, potassium permanganate solution dropwise. The test is negative if no more than 3 drops of the reagent are decolourised. 

The concentration of aqueous solutions of the acid can be deterrnined by titration with sodium hydroxide, and the concentration of formate ion by oxidation with permanganate and back titration. Volatile impurities can be estimated by gas—Hquid chromatography. Standard analytical methods are detailed in References 37 and 38. 

Aqueous potassium permanganate solutions are not perfectiy thermodynamically stable at 25°C, because Mn02, not MnO is the thermodynamically stable form of manganese in water. Thus permanganate tends to oxidize water with the evolution of oxygen and the deposition of manganese dioxide, which acts to further catalyze the reaction. 

Printed circuit boards manufacture is aided by the use of KMnO. Alkaline permanganate solution is used to remove resin smeared on the interior hole wall of multilayered printed circuit boards. Additionally the hole wall is etched, resulting in a surface with excellent adhesion characteristics, for electrodeless copper (250). The alkaline permanganate etchback system containing >60 g/L KMnO and 40-80 g/L NaOH at 70—80°C, is effective for difunctional, tetrafiinctional, and polyimide resin substrates, where the level of etchback is direcdy proportional to the immersion time (10—20 min) (251). 

Silver Permanganate. Silver permanganate [7783-98-4] AgMnO, is a violet soHd formed when a potassium permanganate solution is added to a silver nitrate solution. It decomposes upon heating, exposure to light, or by reaction with alcohol. 

Oxidation of cycHc sulfites with permanganate in acetic acid solution gives cycHc sulfates (102). Heating monohydroxyalkyl hydrogen sulfates with thionyl chlohde causes ring closure (103). 

The precipitated manganese dioxide and sulfur are discarded. The solution is used until it becomes spent or so low in potassium permanganate that it is no longer effective and is discarded and replaced. It is customary to place two scmbbers in series, with the Hquid flow countercurrent to the gas flow, to more efficiendy use the permanganate solution. When the solution in the first scmbber is spent, with respect to the gas, the positions of the scmbbers are... 

We have already noted (Section 4.04.2.1.4(xi)) that alkyl groups on pyrazoles are oxidized with permanganate to carboxylic acids. Silver nitrate and ammonium persulfate transform 4-ethyl-1-methylpyrazole (436) into the ketone (437) (72JHC1373). The best yield was obtained starting with the alcohol (438) and using an acid dichromate solution as oxidizing agent. 

The purification of diethyl ether (see Chapter 4) is typical of liquid ethers. The most common contaminants are the alcohols or hydroxy compounds from which the ethers are prepared, their oxidation products (e.g. aldehydes), peroxides and water. Peroxides, aldehydes and alcohols can be removed by shaking with alkaline potassium permanganate solution for several hours, followed by washing with water, concentrated sulfuric acid [CARE], then water. After drying with calcium chloride, the ether is distilled. It is then dried with sodium or with lithium aluminium hydride, redistilled and given a final fractional distillation. The drying process should be repeated if necessary. 

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