Pyridinium chromate oxidation

Pyridinium chromate on silica ° is also a good general oxidant, even in the presence of acid labile groups. In contrast to PCC on alumina this oxidant may be stored at room temperature for one year, with no loss of activity. It is convenient to use it in the form of a column when performing small scale oxidations the substrate is allowed to stand on the column for a few hours, and tiien the carbonyl compound is obtained simply by eluting the column with a suitable solvent. 

Gelbard et al. have prepared a numbor of neutral and acidic supported ammonium chromates. Neutral resins woe found to be generally more effective dian acidic resins. The large differences in leactiviQr between different unbound, soluble alkylammonium chromates (Section 2.7.6.1) are not so pronounced with the polymer-supported oxidants. Some commoits about the reactivity of these supported oxidants woe made (i) quaternary ammonium salts are more reactive than the tertiary pyridinium chromates (ii) the reactivity of a conqilex chromate XCtOr was found to increase as the basicity of X decreases. Best... 

The procedure is commendable for its sinq>licity, reduced toxicity (chromium in all its oxidation states is carcinogenic) and achieves good yields of ketones from alcohol, for example, octan-2-ol is oxidized into octan-2-one (92%), cyclohexanol into cyclohexanone (90%) and menthol into menthone (98%). Pyridinium chromate is also a well-known oxidant for allylic oxidations. As a silica gel supported reagent, this is turned into an efficient alcohol oxidant that will leave acid-labile functions unscathed. Another advantage of the reagent is the long shelf-life of more than a year. These solid-supported oxidants also greatly facilitate pr uct work-up, when compared with their solution counterparts. 

Several references have appeared on the use of solid-phase oxidants. Solid potassium permanganate-copper sulphate mixtures oxidize secondary alcohols to ketones in high yield, and pyridinium chromate or chromic acid on silica gel are described as convenient off-the-shelf reagents for oxidation of both primary and secondary alcohols. Anhydrous chromium trioxide-celite effects similar transformations only when ether is present as co-solvent. An excellent review, with over 400 references, on supported oxidants covers the use of silver carbonate-celite, chromium trioxide-pyridine-celite, ozone-silica, chromyl chloride-silica, chromium trioxide-graphite, manganese dioxide-carbon, and potassium permanganate-molecular sieve. 

The same type of reactions can be conducted with methyl 2,3,6-tri-O-benzoyl-4-0-trifyl a-D-glucopyranoside to give modified D-galactoses. The free 4-hy-droxyl-carbon can be oxidized with pyridinium chromate to produce the 4-keto derivative, which, in turn, can be fluorinated with DAST to provide the 4-g m-di-fluoride (reaction 4.113). 

Sucrose can be selectively oxidized at C-6 by reacting 2,3,4,l, 3, 4, 6 -hepta-6>-benzoyl sucrose with pyridinium chromate to convert C-6 into an aldehyde. The aldehyde group can be reduced with sodium borohydride to create specifically labeled 6-pH]sucrose (reaction 4.135). 

By Oxidation of Alcohols.—Barium manganate is readily available and stable, and has been recommended for the oxidation of primary and secondary alcohols to aldehydes and ketones respectively. Chromic acid adsorbed on to silica geP and the recyclable poly[vinyl(pyridinium chromate)] effect the same changes, while acid-stable primary and secondary alcohols are oxidized rapidly using potassium dichromate, sulphuric acid, methylene chloride, and a phase-transfer catalyst." Benzeneseleninic anhydride is an alternative reagent for the oxidation of alcohols under essentially neutral conditions. ... 

Oxidation of primary alcohols to aide hydes (Section 15 10) Pyridinium di chromate (PDC) or pyridinium chloro chromate (PCC) in anhydrous media such as dichloromethane oxidizes primary al cohols to aldehydes while avoiding over oxidation to carboxylic acids... 

Primary alcohols are oxidized to either aldehydes or carboxylic acids, depending on the reagents chosen and the conditions used. One of the best methods for preparing an aldehyde from a primary alcohol on a small laboratory scale, as opposed to a large industrial scale, is to use pyridinium chloro-chromate (PCC, CsH NCrO Cl) in dichloromethane solvent. 

The pyridinium chlorochromate (PCC) oxidations of pentaamine cobalt(III)-bound and unbound mandelic and lactic acids have been studied and found to proceed at similar rates.Free-energy relationships in the oxidation of aromatic anils by PCC have been studied. Solvent effects in the oxidation of methionine by PCC and pyridinium bromochromate (PBC) have been investigated the reaction leads to the formation of the corresponding sulfoxide and mechanisms have been proposed. The major product of the acid-catalysed oxidation of a range of diols by PBC is the hydroxyaldehyde. The reaction is first order with respect to the diol and exhibits a substantial primary kinetic isotope effect. Proposed acid-dependent and acid-independent mechanisms involve the rapid formation of a chromate ester in a pre-equilibrium step, followed by rate-determining hydride ion transfer via a cyclic intermediate. PBC oxidation of thio acids has been studied. ... 

Following earlier studies of the oxidation of formic and oxalic acids by pyridinium fluoro-, chloro-, and bromo-chromates, Banerji and co-workers have smdied the kinetics of oxidation of these acids by 2, 2Tbipyridinium chlorochromate (BPCC) to C02. The formation constant of the initially formed BPCC-formic acid complex shows little dependence on the solvent, whilst a more variable rate constant for its decomposition to products correlates well with the cation-solvating power. This indicates the formation of an electron-deficient carbon centre in the transition state, possibly due to hydride transfer in an anhydride intermediate HCOO—Cr(=0)(0H)(Cl)—O—bpyH. A cyclic intermediate complex, in which oxalic acid acts as a bidentate ligand, is proposed to account for the unfavourable entropy term observed in the oxidation of this acid. 

Pyridinium and quaternary ammonium resins react with chromium trioxide, producing polymer-supported complex chromates that oxidize alcohols, and provide a very facile work-up.427... 

Kinetics and activation parameters for the oxidation of phenol with tetrakis(pyridine) cobalt(II) chromate have been determined.16 The oxidation of oximes of cyclopen-tanone, cyclohexanone, and cycloheptanone with pyridinium fluorochromate is first order each in the oxidant and oxime. The observed reactivity sequence has been rationalized on the basis of I-strain.17... 

Oxidation of 2,3-O-eyclohexylidcne-D-ribose by pyridinium chloro-chromate gave 2,3-O-cyclohexylidene-D-ribonono-1,4-lactone in 55-60% yield.23... 

Oxidation of alcohols is normally carried out with Cr(VI) reagents (Chapter 24) but these, like the Jones reagent (Na2Cr2C>7 in sulfuric acid), are usually acidic. Some pyridine complexes of Cr(Vl) compounds solve this problem by having the pyridinium ion (p Ta 5) as the only acid. The two most famous are PDC (Pyridinium DiChromate) and PCC (Pyridinium Chloro-Chromate). Pyridine forms a complex with CrO but this is liable to burst into flames. Treatment with HC1 gives PCC, which is much less dangerous. PCC is particularly useful in the oxidation of primary alcohols to aldehydes as overoxidation is avoided in the only slightly acidic conditions (Chapter 24). 

An alternative tt> the chromium trioxide-pyridine comidex is provided by pyridinium chlorochromate (PCC) and pyridinium dichromate (PDC). These reag ts, now ubiquitous for chromate-based oxidation of alcohols, overcome the hygroscofric nature of the chromium trioxide-i ridine complex and are prepared by a less hazardous procedure both are commercially available as are several other derivative reagents. 

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