Permanganate oxidation with

By oxidation with permanganate it forms pinonic acid, C,oH,<503, a monobasic acid derived from cyclobutane. With strong sulphuric acid it forms a mixture of limonene, dipentene, terpinolene, terpinene, camphene and p-cymene. Hydrogen chloride reacts with turpentine oil to give CioHijCl, bomyl chloride, artificial camphor . 

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. 

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. 

Terephthalic acid has been obtained from a great many /)-disubstituted derivatives of benzene or cyclohexane by oxidation with permanganate, chromic acid, or nitric acid. The following routes appear to have preparative value from />-toluic acid, />-methylacetophenone,2 or dihydro-/)-tolualdehyde by oxidation with permanganate from f>-cymene by oxidation with sodium dichromate and sulfuric acid from />-dibromobenzene or from /i-chloro- or -bromobenzoic acid by heating at 250° with potassium and cuprous cyanides and from />-dibromo-benzene, butyllithium, and carbon dioxide. ... 

Permanganate value Legislation and controls Oxidation with permanganate... 

On oxidation with permanganate, methylharmaline is converted into a neutral substance, CiaHj O Na, m.p. 228°, which, on reduction with sodium and n-butyl alcohol yields A -methyltetrahydronorharmine (XVII),... 

While this work was in progress Spath and Bretschneider showed that strychnine, on oxidation with permanganate in alkaline solution, furnished W-oxalylanthranilic acid (VII), brucine yielding oxalyl-4 5-dimethoxy-anthranilic acid, the latter observation providing confirmation of the evidence previously adduced that the two methoxy-groups in brucine are in the oj Ao-position relative to each other as indicated by Lions, Perkin and Robinson. The results so far considered indicate the presence in brucine and strychnine of the complex (VIII), which can be extended to (IX) if account is taken of the readiness with which carbazole can be obtained from strychnine and brucine and certain of their derivatives by decomposition with alkali at temperatures ranging from 200° to 400°, Knowledge of the structure of the rest of the molecule is mainly due to the results of the exhaustive study by Leuchs and his pupils of the oxidation... 

The unsaturated diamine, CgHgoNj, from the hydrolysis of sphero-physine, on oxidation with permanganate yields the ketoaldehyde, McgCH. CO. CHO fdioxime, m.p. 95-6°, and osazone, m.p. 113-4°) and putrescine, NH2[CH2]4NH2, which indicates that this unsaturated diamine is Me2CH. CH CH. NH[CH2]4. NH2. 

Ewins has synthesised both substances from m-methoxybenzoic acid, which on nitration gave 2-nitro-3-methoxybenzoic acid, and this, on reduction and treatment with methyl iodide, yielded damasceninic acid, which, by esterification with methyl alcohol, furnished damascenine. Kaufmann and Rothlen found that the additive product of 8-methoxy-quinoline and methyl sulphate, on oxidation with permanganate, yields formyldamasceninic acid, MeO. CgH3(NMe. CHO). COOH, which can be transformed into damasceninic acid by warming with dilute hydrochloric acid. ... 

In the key step, oxidation with permanganate in acetone leads from the sulfenamide to the sulfonamide. There is thus obtained ethoxysolamide (73). ... 

The presence of lerpineue conld not be proved. No fraction gave the nitrite reaction, and auv considerable quantity ot phellandrene is therefore Out of ihc question. Tbe results ot the oxidation with permanganate indicetc the preseuc.- ot -phellandrene, which proves that when small quantities ot phellandrene are present, identibcatiou by the nitrite reaction is very oficn a failure. 

The isopinene used in subsequent researches was obtained by fractionating the pinolene boiling at 144° to 145° C., a mixture of the o- and /3-isomeride, then treating it with hydrogen chloride and removing this acid by means of aniline. The hydrocarbon obtained was purified by oxidation with permanganate in acetone solution. It possesses the following constants —... 

On oxidation with permanganate of potassium it yields sabinol-glycerine, CjoH,5(011)3, melting at 152° to 153°, and by further oxidation, tanacetogene-dicarboxylic acid, CpHj Og, melting at 140°. On reduction with sodium and amyl alcohol, sabinol yields thujyl alcohol, CjoHj OH. 

On oxidation with permanganate of potassium, this phenol ether yields tetramethoxy benzoic acid, C H(OCH3)4COOH, melting at 87°. 

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