Oxidation, amines carboxylic acids

An alternative procedure for oxidation to ketones involves treatment of the alkylborane with a quaternary ammonium perruthenate salt and an amine oxide186 (see Entry 6 in Scheme 4.9). Use of dibromoborane-dimethyl sulfide for hydroboration of terminal alkenes, followed by hydrolysis and Cr(VI) oxidation gives carboxylic acids.187... 

The starting material is an 18 electron nickel zero complex which is protonated forming a divalent nickel hydride. This can react further with alkenes to give alkyl groups, but it also reacts as an acid with hard bases to regenerate the nickel zero complex. Similar oxidative addition reactions have been recorded for phenols, water, amines, carboxylic acids, mineral acids (HCN), etc. 

Liquid Peroxyoxalates Oxidants (H202, etc.) Fluorophores (polycyclic aromatic hydrocarbons, etc.) Derivatized compounds with fluorophores (amino acids, steroids, aliphatic amines, carboxylic acids, catecholamines, etc.)... 

Reactions have been described for RH = amines, alcohols, aromatics, aliphatics, perfluoroalkyls, hydrogen halides, and thiols (167). Another recent use of S2OfiF2 in organic chemistry has been in the synthesis of lactones by the remote oxidation of carboxylic acids using a... 

It has been found that the end groups play a major role in the rate of oxidation since carboxylic acid groups will catalyse decomposition of hydroperoxide and lower the temperature for the maximum rate of degradation by 60 C. In contrast polyamides terminated with amine end groups are more stable. 

CHEMICAL PROPERTIES Combustible liquid polymerizes above 392 F reacts vigorously with water, strong acids, strong bases, amines, carboxylic acids and organotin, heat, strong oxidizers FP (140°C) AT (454°F) LFL (0.9%) UFL (9.5%). 

Dehydrogenases and Oxidases An alcohol dehydrogenase oxidizes alcohols to aldehydes, which in turn are oxidized to carboxylic acids by an aldehyde dehydrogenase. Amine oxidases catalyze the oxidation of primary amines to alcohols. 

Applications of IBX in organic synthesis have been summarized in several comprehensive reviews [1105, 1106], IBX is a particularly useful oxidant for the selective oxidation of alcohols to carbonyl compounds, even in complex molecules in the presence of other functional groups. Primary alcohols are oxidized by IBX in DMSO to the corresponding aldehydes at room temperature without overoxidation to the acids. The chiral primary alcohols are oxidized without epimerization and various functional groups like thioethers, amines, carboxylic acids, esters, carboxamides and both conjugated and isolated double bonds are compatible with IBX [1132,1133]. Several representative examples of alcohol oxidations using IBX in DMSO are shown below in Schemes 3.330-3.335. 

For example, a number of potentially useful iron-chelating drugs are derivatives of phenols, carboxylic acids, and amines. Carboxylic acids, being a metabolic end product, are stable to microsomal oxidation but are subject to conjugation. Phenols are similarly subject to conjugation and also to microsomal hydroxyla-tlon. Amines are subject to conjugation (if primary or secondary), and to oxidation and N-dealkylation. 

Precaution Incompat. with water, amines, carboxylic acid, alcohols, and strong oxidizing materials... 

Properties Colorless liq. sp.gr. 1.06 g/cm dens. 8.8 Ib/gal vise. 100-250 cps flash pt. (Seta) 31 C 75 1% solids Precaution Incompat. with water, amines, carboxylic acid, alcohols, and strong oxidizing materials... 

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