Ketone alkene

Peroxomonosulfuric acid oxidi2es cyanide to cyanate, chloride to chlorine, and sulfide to sulfate (60). It readily oxidi2es carboxyflc acids, alcohols, alkenes, ketones, aromatic aldehydes, phenols, and hydroquiaone (61). Peroxomonosulfuric acid hydroly2es rapidly at pH <2 to hydrogen peroxide and sulfuric acid. It is usually made and used ia the form of Caro s acid. 

Hydroperoxides have been obtained from the autoxidation of alkanes, aralkanes, alkenes, ketones, enols, hydrazones, aromatic amines, amides, ethers, acetals, alcohols, and organomineral compounds, eg, Grignard reagents (10,45). In autoxidations involving hydrazones, double-bond migration occurs with the formation of hydroperoxy—azo compounds via free-radical chain processes (10,59) (eq. 20). 

CH3SCH3, CH3CN, (PhC0>202, 0°, 2 h, 75-95% yield. Acetonides, THP ethers, alkenes, ketones, and epoxides all survive these conditions. 

For the oxidation of allylic alcohols to alkene ketones, see Section 168 (Ketones from Alcohols and Phenols)... 

For the alkylation of alkene ketones, also see Section 177 (Ketones from Ketones) and for conjugate alkylations see Section 74E (Alkyls form Alkenes). 

DCA forms canal inclusion compounds, known as choleic acids, which most frequently have the orthorhombic space group P212121, or less frequently Pl l. In such crystals the DCA molecules hydrogen bond to each other to form an extended bilayer structure, thereby creating a hydrophobic canal between adjacent bilayers. The guest molecules present in these canals therefore tend to be non-polar or moderately polar molecules such as aromatic compounds, alkenes, ketones and certain carboxylic acids 92). Since the bilayers are held together only by van der Waals forces the canals are able to adopt different dimensions to accommodate the variety of... 

A range of addition reactions of (TMS)3GeH with alkynes, alkenes, ketones, azines, and quinones has been studied using EPR. In addition, synthetic studies of hydrogermylation of alkynes have shown that the reaction proceeds regio- and stereo-selectively, whereas reactions with alkenes do not take place (presumably owing to the reversibility of the germyl radical addition) (Scheme 29). 

Preparation of alkenes Ketone reacts with phosphorus ylide to give alkene. By dividing a target molecule at the double bond, one can decide which of the two components should best come from the carbonyl, and which from the ylide. In general, the ylide should come from an unhindered alkyl halide since triphenyl phosphine is bulky. 

The order of reactivities of various functional groups determined under standard conditions (using externally generated diborane, and tetrahydrofuran as solvent) is acid > alkene > ketone > nitrile > epoxide > ester > acid chloride.33 Acids, aldehydes, ketones, epoxides, nitriles, lactones and azo compounds are reduced rapidly, esters more slowly and chloral, acid chlorides and nitro compounds are inert. Double bonds undergo the hydroboration reaction,25 nitriles and azo compounds are reduced to amines, and the remaining groups to alcohols. Ketones can be reduced selectively in the presence of epoxides. Contrary to the order of reactivities given above, it has been claimed that nitriles are reduced more rapidly than ketones.223... 

IrCI(CO)(PCy3)2] Alkenes, activated alkenes, ketones... 

Reactions with electrophilic alkenes, ketones and ketenes 709... 

Mixed chromophores with both C=C and C=0 moieties such as ,/3-unsaturated enones are one of the most investigated chromophores in organic photochemistry. Conjugation of the two chromophoric moieties results in lowering the n —> ji and tt ji energy levels relative to the unconjugated chromophores. UV absorption spectra of selected alkenes, ketones and enones are presented in Table 1. 

Polyphenylsilane, (PhSiH) , can be derivatized by free-radical hydrosilylation in the presence of a radical initiator. Alkenes, ketones and aldehydes react readily, to replace up to 93% of the Si-H bonds. This route can be employed to make polysilanes with hydrophilic groups, such as hydroxy, amino and carboxylic acid functions.43 Dialkylamino substituted polysilanes, made by the anionic polymerization of masked disilenes (see equation (17)), when treated with acetyl chloride give chloro-substituted poly silanes. The chlorine can then be displaced by other nucleophiles.27... 

The catalytic, asymmetric hydrogenations of alkenes, ketones and imines are important transformations for the synthesis of chiral substrates. Organic dihydropyridine cofactors such as dihydronicotinamide adenine dinucleotide (NADH) are responsible for the enzyme-mediated asymmetric reductions of imines in living systems [86]. A biomimetic alternative to NADH is the Hantzsch dihydropyridine, 97. This simple compound has been an effective hydrogen source for the reductions of ketones and alkenes. A suitable catalyst is required to activate the substrate to hydride addition [87-89]. Recently, two groups have reported, independently, the use of 97 in the presence of a chiral phosphoric acid (68 or 98) catalyst for the asymmetric transfer hydrogenation of imines. 

The catalytic hydrogenation of alkenes, ketones, and imines is arguably one of the most important transformations in chemistry. Powerful asymmetric versions have been realized that require metal catalysts or the... 

It is worth noting at this point that palladium(II) salts intervene in a synthetically useful way when alkenes are reacted with Hg" salts in either water or alcohols. Thus oxymercuration-palladation— depalladation ensues and results in alkene -> ketone conversions (equation 18). The reaction can be catalytic in Pd, if a reoxidant such as Cu" is employed. 

Unsaturated organic compounds such as aUcynes, alkenes, ketones, oximes, nitriles, and imines, are readily reduced by H2 using a catalyst for example ... 

Since its discovery in 1912, the Claisen rearrangement of allyl vinyl ethers (1 - 2 equation 1) has become one of the most powerful tools for stereoselective carbon-carbon bond formation. Much of its current popularity is due to the subsequent development of a series of new variants of this 3,3-sigma-tropic rearrangement. In 1940, Carroll reported the base-catalyzed rearrangement of -keto esters and allylic alcohols to alkenic ketones (3 4 5 equation 2). Twenty years later. Saucy and Marbet dem-... 

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