Permanganate as oxidant

The oxidation of diethyl 3,6-hexanooxepin-4,5-dicarboxylate with a mixture of sodium periodate and potassium permanganate as oxidizing agent gives diethyl 3-[(formyioxy)methylene]-l 0-oxocyclodec-l-en-l,2-dicarboxylate (2) in 91 % yield.130 A minor modification of the reaction conditions gives two products 2 (35 %) and a product which retains the oxepin structure (23 %) identified as the same lactone described in Section 1.2.1.1.129... 

An early study of the attempted phase-transfer catalysed oxidation of dibenzyl sulphoxide to the sulphone using a variety of conditions and oxygen, periodate, hypochlorate and permanganate as oxidants showed that only potassium permanganate gave any of the required product, albeit in low yields. A further study, using Adogen 464 as... 

To prepare 2-aminopyridine by treatment of pyridine with potassium amide in liquid ammonia at —33 °C and using permanganate as oxidant was not successful. No reaction takes place under these conditions. The aromaticity of the pyridine ring is too high to allow nucleophilic amide addition. It was surprisingly observed that treatment of a solution of 3-nitropyridine in liquid ammonia (thus without the presence of potassium amide) with potassium permanganate, gave after work-up a mixture of... 

In the oxidative amination of quinoline, using potassium amide in liquid ammonia and permanganate as oxidant, it was found that the site of ami-nation is strongly depending on temperature. When the amination is carried out at — 65 °C 2-aminoquinoline is isolated (52%) 4-aminoquinoline is formed (with some 2-aminoquinoline) when the amination is performed at room temperature. By NMR spectroscopy it was unequivocally observed that at — 65 °C addition of the amide ion occurs at position 2 of the quinoline ring, yielding the a-adduct 2-amino-1,2-dihydroquinolinide, which under the conditions of the reaction remained stable. When warming up the solution this C-2 adduct irreversibly converts into the... 

Extension of this work by studying the oxidative methylamination of 5-, 6-, and 7-nitroquinoxalines, using liquid methylamine at room temperature and permanganate as oxidant, gives, as could be expected, similar results to those obtained in the oxidative amination (Scheme 23) (94IJHC75). 

Oxidative alkylamination of pteridine and its 2-chloro, 7-aryl, or 7-/-Bu derivative, using an alkylamine (Alkyl = Et or t-Bu) and potassium permanganate as oxidant, gave the corresponding 4-alkylamino pteridines (Scheme 32) (82JHC1527, 86JHC843). 

Quinoxaline (235) has been easily aminated in liquid ammonia with excess potassium amide and potassium permanganate as oxidant (82JHC1285). The ratio of monoamino to diamino products can be altered by varying the reaction time prior to addition of the oxidant (Scheme 78). When potassium permanganate was added 5-10 min after 235 was added to liquid ammonia containing potassium amide, the yield of 2-aminoquinoxaline (236) was 53% and 2,3-diaminoquinoxaline(237) was 23%. However, if the oxidant was not added until 30 min had elapsed, the yield of 236 was 4% and that of 237 was 57%. 

Aliphatic nitro-compounds, as their nitronate anions, react with molybdenum peroxide, MoO5.py.HMPA, to give carbonyl compounds. Primary nitroalkanes give the carboxylic acid. A re-appraisal of potassium permanganate as oxidant for primary nitroalkane salts indicates this can be an excellent reagent for the preparation of aldehydes, particularly quaternary aldehydes. ... 

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