Oxidation permanganate/periodate

Unsaturated acids may be split chemically at their double bonds. Permanganate-periodate oxidation has been used to produce the corresponding carboxylic acids, while an alternative technique of ozonolysis results in the formation of aldehydes and aldehyde esters. All these reaction products may be identified by GLC and the information used to determine the position of the double bond in the original fatty acid. 

Another chemical route is based on the work of Kakinuma et al. (38), who synthesized the two chiral, deuterated epoxides shown in Scheme S. Separation of the two diastereomers and reductive epoxide ring opening with tritiated LiAlH4 followed by permanganate/periodate oxidation gave acetic acid which within the limits of detection was chirally pure (100 7% e.e.) (39). 

Permanganate/periodate oxidation of 11 afforded the diacid 12, having the bicyclooctane structure with the correct relative configuration of the chiral centers. 

A structure (LXXXII) for anhydroryanodine (see Volume V, p. 321) has been proposed (216) on the basis of IR-, UV-, and NMR-spectro-scopy supplemented by some chemical reactions. Ryanodol is the non-nitrogenous fragment obtained by the hydrolysis of ryanodine. Mild acid treatment converted it into a lactone. Permanganate-periodate oxidation yielded acetic, isobutyric, and -methylglutaric acids. The NMR-spectrum showed that there are six hydroxy groups, only one being secondary, in addition to the hemiacetal function. The remainder were tertiary (217). 

It must be recalled that the determination of the dicarboxylic acids generated by permanganate-periodate oxidation of monoenoic fatty acids was useful to study the position of the double bond in the carbon chain. 

The conversions of 1-C -palmitic acid to l-C -palmitoleic acid and stearic acid to oleic acid were effected aerobically in the presence of CoA, ATP, TPNH, and Mg++. Oxygen could not be replaced by electron acceptors such as methylene blue, FAD, or ferricyanide. When palmityl-CoA was used as substrate, desaturation required only the particulate fraction of yeast homogenate, TPNH, and oxygen. The reaction was stimulated by cyanide ions, inhibited by cytochrome c, but not by catalase. These properties are typical for hydroxylases of the mixed function transferase category (Mason, 1957). Proof of the location of the double bond between C-9 and C-10 was established by permanganate-periodate oxidation of palmitoleic acid and the isolation of azelaic acid. 

Cleavage of an alkenoic acid can be carried out with permanganate, a permanganate—periodate mixture, periodate or with nitric acid, dichromate, ozone, or, if the unsaturation is first converted to a dihydroxy compound, lead tetraacetate (71,73). Oxidative ozonolysis is a process for the manufacture of azelaic acid [123-99-9] and pelargonic acid (74). 

Oxidation. Citric acid is easily oxidized by a variety of oxidizing agents such as peroxides, hypochlorite, persulfate, permanganate, periodate, hypobromite, chromate, manganese dioxide, and nitric acid. The products of oxidation are usually acetonedicarboxyhc acid (5), oxaUc acid (6), carbon dioxide, and water, depending on the conditions used (5). 

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... 

As discussed in connection with cleavage of double bonds by permanganate-periodate or osmium tetroxide-periodate (see p. 757), the glycol unit is susceptible to oxidative cleavage under mild conditions. The most commonly used reagent for this oxidative cleavage is the periodate ion.150 The fragmentation is believed to occur via a... 

The position and geometry of the side chain double bonds can be determined by ozonolysis and a potassium permanganate-sodium periodate oxidation, as well as by the IR spectrum. Results have shown that the side chain double bonds are always Z 16,122,126). 

The effects of such oxidants as a mixture of potassium iodate and dichromate in concentrated sulfuric and phosphoric acids (van Slyke reagent), hot solutions of chromic acid, and acidic solutions of ceric sulfate, permanganate, periodate, and hyperoxidized transition metals on a number of sugar derivatives has been described (Ref. 1, pp. 1151-1153). 

Oxidation of the pyrazole carboxaldehydes 294 using potassium permanganate in aqueous pyridine gave satisfactory yields of the carboxylic acids 295 (Equation 56) <2001CHE467>. Condensation of AT-alkylpyrazole-4-carbaldehyde 296 with 2,3-bis(hydroxyamino)-2,3-dimethylbutane sulfate, then sodium periodate oxidation of 1,3-dihydroxyimi-dazolidine 297 afforded pyrazolyl nitronyl nitroxides 298 (Scheme 26) <2001ARK55>. Another approach to... 

This characteristic component of the phytosphingolipids gives L-serine phosphate on oxidation with permanganate and hydrolysis, followed by periodate oxidation. 

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