Carbonyl chromium complexes carboxylic acid

Carboxylic acids, a-bromination of 55, 31 CARBOXYLIC ACID CHLORIDES, ketones from, 55, 122 CARBYLAMINE REACTION, 55, 96 Ceric ammonium nitrate [Ammonium hexa mtrocerate(IV)[, 55, 43 Chlorine, 55, 33, 35, 63 CHROMIUM TRIOXIDE-PYRIDINE COMPLEX, preparation in situ, 55, 84 Cinnamomtnle, a-phenyl- [2-Propeneni-tnle 2,3-diphenyl-], 55, 92 Copper(l) iodide, 55, 105, 123, 124 Copper thiophenoxide [Benzenethiol, copper(I) salt], 55, 123 CYCLIZATION, free radical, 55, 57 CYCLOBUTADIENE, 55, 43 Cyclobutadieneiron tricarbonyl [Iron, tn-carbonyl(r)4-l,3-cyclo-butadiene)-], 55,43... 

A common way to change reaction conditions for the oxidation of alcohols is to modify the acid that is added to the medium. Indeed, chromium trioxide will have different oxidizing abilities in different acids. Since most organic compounds are insoluble in water, a cosolvent is usually required to dissolve not only the chromium reagent but also the alcohol substrate. This solvent must be resistant to oxidation, and acetic acid or acetone are commonly used. For the alcohol - carbonyl conversion several Cr(VI) reagents can be used, including chromium trioxide in water or aqueous acetic acid catalyzed by mineral acid, sodium dichromate in aqueous acetone catalyzed by mineral acid, sodium dichromate in acetic acid, the Cr03 pyridine complex, and err-butyl chromate.Both primary and secondary alcohols can be oxidized to the aldehyde or ketone, respectively. Aldehydes may be oxidized to the carboxylic acid under some conditions. 

The use of chromium(VI) reagents as oxidants is limited by their inherent toxicity, the need to prepare them in various complex forms (with acetic acid or pyridine), and complicated work-up procedures. Chromium trioxide (Cr03) immobilized on pre-moistened alumina affords efficient oxidation of benzyl alcohols to carbonyl compounds by simple mixing. Remarkably, neither the over-oxidation to carboxylic acids nor the usual formation of tar, a typical occurrence in many CrOj oxidations, is observed [108]. The reagent system is also used for the preparation of acyclic a-nitro ketones by the oxidation of nitroalkanols under solvent-free conditions [109]... 

Other methods for ketene generation that are occasionally used are conceptually similar to the elimination of acyl chlorides but use different carboxyl activating groups. Activation of a carboxylic acid by Mukaiyama s reagent, for example, followed by treatment with triethylamine to generate a ketene in situ, has been used on occasion. A very mild method for ketene formation involves treatment of the carboxylic acid with triphenylphosphine and carbon tetrabromide in the presence of the imine. The photolysis of metal-carbene complexes, particularly chromium carbonyl carbenes, has been used but this necessarily involves more effort in the preparation of the necessary ketene precursor. ... 

Catalysts suitable specifically for reduction of carbon-oxygen bonds are based on oxides of copper, zinc and chromium Adkins catalysts). The so-called copper chromite (which is not necessarily a stoichiometric compound) is prepared by thermal decomposition of ammonium chromate and copper nitrate [50]. Its activity and stability is improved if barium nitrate is added before the thermal decomposition [57]. Similarly prepared zinc chromite is suitable for reductions of unsaturated acids and esters to unsaturated alcohols [52]. These catalysts are used specifically for reduction of carbonyl- and carboxyl-containing compounds to alcohols. Aldehydes and ketones are reduced at 150-200° and 100-150 atm, whereas esters and acids require temperatures up to 300° and pressures up to 350 atm. Because such conditions require special equipment and because all reductions achievable with copper chromite catalysts can be accomplished by hydrides and complex hydrides the use of Adkins catalyst in the laboratory is very limited. 

---