Alcohols periodic acid oxidation

Hercules Method D90-3e (Ref 17, pll). Nitroglycerin by Periodic Acid Oxidation. NG and some other nitrate nitrogen esters which may be present in expl oils can be quantitatively denitrated to their, respective alcohols by action of methanol and coned HCl. On oxidizing the residue of polyhydric alcohols with periodic acid, H5I06, the secondary carbon and alcohol group in glycerin are oxidized to formic acid,... 

The Malaprade Periodic Acid Oxidation Reaction oxidizes 1,2 diols or 2-amino alcohols with periodic acid ... 

Hofmann degradation of the nonnatural protoberberine 454 afforded the 10-membered ring base 455 (65%) in addition to the styrene-type compound (13%) (Scheme 92). Dihydroxylation of the former with N-bromosuccinimide in the presence of a large excess of hydrochloric acid and subsequent oxidation of the product diol 456 with periodic acid afforded the dialdehyde 457. On irradiation in tert-butyl alcohol 457 provided ( )-cis-alpinigenine (445) along with ( )-alpinigenine (441) as a result of endo and exo intramolecular cycloaddition, respectively, of the intermediate photodienol (221,222). 

Poly(vinyl acetate) of number-average molecular weight 100,000 is hydrolyzed to poly(vinyl alcohol). Oxidation of the latter with periodic acid to cleave 1,2-diol linkages yields a poly(vinyl alcohol) with Xn = 200. Calculate the percentages of head-to-tail and head-to-head linkages in the poly(vinyl acetate). 

The ready condensation of sucrose with excess triphenylmethyl chloride in pyridine to a tri-trityl ether is, however, more easily explained by XV or II, which have three, instead of two (c/. I), primary alcohol groups to react selectively in the condensation. Fleury and Courtois oxidized sucrose for twenty-four hours at 14° with an excess of suitably buffered periodic acid and found that three moles of the oxidant were consumed and one mole of formic acid was eliminated. This highly selective oxidant is known to cleave unsubstituted 1,2 glycols quantitatively to two carbonyl groups and to eliminate the center carbon atom... 

Oxidative Degradation of Poly(vinyl Alcohol) with Periodic Acid... 

It is of interest that the methyl alcohol 81 underwent oxidation with chromic acid to afford 3-acetylfervenulin 83 in good yield, whereas the same conditions resulted in the conversion of alcohol 79 into fervenulin 8. The desired product of this latter transformation, that is, fervenulin-3-carboxaldehyde 82, could, however, be obtained, albeit in low yield, by the oxidation of alcohol 79 with manganese dioxide. Fervenulin-3-carboxaldehyde 82 could be obtained in much better yield from the treatment of 3-styrylfervenulin 68 with periodate in the presence of osmium tetroxide, or by ozonolysis of the same substrate. 

There may be circumstances such that oxidation of an alcohol to the ketone with Cr is warranted. Mark Trudell of the University of New Orleans reports (Tetrahedron Lett. 44 2553, 2003) that such oxidations can be carried out with catalytic Cr and stoichiometric periodic acid, as illustrated by the conversion of 10 to 11. 

Our observations are summarized as follows (1) no induction period, (2) fast alcohol oxidation in an oxygen-poor liquid phase, (3) no carboxylic acids from the higher alcohols, (4) slow oxidation of lauryl aldehyde to lauric acid in the presence of water, and (5) recovery of bromine in the organic phase on reaction completion. These data show that the reaction is not a radical chain process but rather a bromine oxidation in which the halogen is continuously regenerated, as shown in Reactions 1 through 7. 

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