Alcoholic carbonyl compounds

A closely related method does not require conversion of enantiomers to diastereomers but relies on the fact that (in principle, at least) enantiomers have different NMR spectra in a chiral solvent, or when mixed with a chiral molecule (in which case transient diastereomeric species may form). In such cases, the peaks may be separated enough to permit the proportions of enantiomers to be determined from their intensities. Another variation, which gives better results in many cases, is to use an achiral solvent but with the addition of a chiral lanthanide shift reagent such as tris[3-trifiuoroacetyl-Lanthanide shift reagents have the property of spreading NMR peaks of compounds with which they can form coordination compounds, for examples, alcohols, carbonyl compounds, amines, and so on. Chiral lanthanide shift reagents shift the peaks of the two enantiomers of many such compounds to different extents. 

Many oxygenated monoterpenes (alcohols, carbonyl compounds, esters) serve as fragrances. Here inexpensive natural starting compounds are a-pinene (4), /1-pinene (5) and limonene (6), with production volumes of about 18000, 12 000, and 30000 t a-1, respectively. 

Oxidation of Oxygen-containing Compounds (Alcohols, Carbonyl Compounds, Carboxylic Acids)... 

The anode is an ideal reagent to oxidize organic substrates such as oxygen-containing compounds (alcohols, carbonyl compounds, and carboxylic acids). Thereby these substrates can be converted avoiding chemical reagents, which simplifies the reaction conditions and the work-up. Additionally, the electron transfer leads selectively to a variety of reactive species, which can find further use in organic synthesis. 

This article shows a variety of patterns of electrochemical oxidation of oxygen-containing compounds (alcohols, carbonyl compounds, and carboxylic acids), aiming to be helpful for both electroorganic and organic chemists to cover this field from a synthetic viewpoint. Since there have been excellent books [1-5] published on the subject, this article quotes only some typical and important papers from before 1990. 

A Hylic alcohols Carbonyl compounds Ru, Rh or Pd with TPPTS or 34 (n=3,niR0) [10]... 

Alcohols carbonyl compounds acetate buffer, room temperature 169... 

SiWiiO39Mn(H2O) - Alcohols carbonyl compounds Electrolysis, phosphate buffer (lUlpH 6) 1.25 V vs. Ag/AgCl, divided cell, room temperature, C anode, Pt cathode 153g-hh... 

The oxidation of olefins can result in the formation of organic hydroperoxides. These compounds readily decompose to form alcohols, carbonyl compounds, and other oxidized species. These oxidized hydrocarbons can further react to form highly cross-linked, oxygen-rich materials. Some of these species can adhere to metal surfaces to form a hard vamishlike film or coating on metal parts. This varnish can act as a site for further deposition and eventual corrosion of metal. In severe cases, varnish can interfere with the hydrodynamic lubrication of moving metal parts and efficiency of component operation. 

Hydroperoxide formation is characteristic of alkenes possessing tertiary allylic hydrogen. Allylic rearrangement resulting in the formation of isomeric products is common. Secondary products (alcohols, carbonyl compounds, carboxylic acids) may arise from the decomposition of alkenyl hydroperoxide at higher temperature. 

Termination of the autoxidation chain process occurs as peroxyl radicals couple to yield non-radical products. This reaction takes place through an unstable tetroxide intermediate. Primary and secondary tetroxides decompose rapidly by the Russell termination mechanism to yield three non-radical products via a six-membered cyclic transition state (Fig. 95). The decomposition yields the corresponding alcohol, carbonyl compound, and molecular oxygen (often in the higher energy singlet oxygen state) three... 

Acids Esters Alcohols Carbonyl compounds Others... 

Terpenoids can be classified also into hydrocarbons, alcohols, carbonyl compounds, phenols, acids, esters, oxides, and peroxides. 

In the presence of dioxygen, the carbon radical R- produced by reactions (201) and (202) ar transformed into alkylperoxy radicals ROO, reacts with Co or Mn species to regenerate th Co " or Mn " oxidants, and produce primary oxygenated products (alcohol, carbonyl compounds which can be further oxidized to carboxylic acids. This constitutes the basis of several Industrie processes such as the manganese-catalyzed oxidation of n-alkenes to fatty acids, and the cobal catalyzed oxidation of butane (or naphtha) to acetic acid, cyclohexane to cyclohexanol-on mixture, and methyl aromatic compounds (toluene, xylene) to the corresponding aromatic monc or di-carboxylic acids. ... 

Amide, aniline or alcohol, carbonyl compound, Na2S04 (leq. molar/substrate) and Pd/C 10% (2. 5% molar/substrate) were mixed in the... 

The oxidation of saturated hydrocarbons by alkyl hydroperoxides catalyzed by various metal complexes yields alcohols, carbonyl compounds (ketones and aldehydes) and peroxides. Examples of recent works devoted to these reactions are given in Table X.3. Usually ferf-butyl hydroperoxide is employed for these oxidations. Other hydroperoxides, e.g., cumyl hydroperoxide [38a, 42a], have been also reported to oxygenate alkanes. 

A wide range of alcohols, carbonyl compounds (particularly if the carbonyl group is close to the stereogenic center), lactones, phosphorus compounds, aromatic compounds, and sulfoxides have been successfully resolved on the different poly(saccharide) derivatives, Non-polar mobile phases are commonly used, although not exclusively, and the selectivity of the various cellulose polymers changes with the character of the ester or carbamate groups used to derivatize the polymer. 

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