Alcohol ates

Secondary alcohols ate oxidi2ed to ketones in good yields under mild conditions in a triphasic system using an inert solvent, soHd Ca(OCl)2, and a hypochlorite resin as catalyst (175). 

UV-VIS Unless the molecule has other chromophores, alcohols ate transpaient above... 

On vigorous reaction with basic reagents (sodium hydroxide or sodium alcohol-ate), a nitro group located symmetrically, in the meta position to other nitro groups... 

The same compounds can be obtained by the action of the corresponding alcohol-ates, through the formation of intermediate addition products ... 

Certain aryl-substituted a- and /S-amino Intones have been successfully reduced to amino alcohols by catalytic hydrogenation over palladium, platinum, or nickel catalysts. Cleavage of the carbon chain sometimes occurs during catalytic hydrogenation of /S-amino ketones. Fair yields of the amino alcohols ate obtained in these cases by reduction with sodium amalgam in dilute acid or aluminum amalgam and water. /S-Amino aldehydes from the Mannich reaction (method 444) are reduced in excellent yields to amino alcohols by lithium aluminum hydride or by catalytic hydrogenation over Raney nickel. Lithium aluminum hydride reduces diazo ketones to 1-amino-2-alkanols (93-99%)- ... 

Nitro alcohols ate usually isolated (method 102) but are sometimes dehydrated directly to olefinic nitro compounds as in the preparation of co-nitro-2-vinylthiophene from nitromethane, thiophenecarboxaldehyde, and sodium hydroxide (78% yield). Many substituted /3-nitrostyrenes have been obtained by condensation of nitromethane or nitroethane with substituted benzaldehydes. A methyl group on the benzene ring is sufficiently activated by nitro groups in the orlio or para position to cause condensation with aldehydes. A series of nitrostilbenes has been made in this way from substituted benzaldehydes. ... 

The plasticizer range alcohols ate utilized primarily in plasticizers, but they also have a wide range of uses in other industrial and consumer products, as... 

Substitution. Secondary aUyUc alcohols ate converted to amines by reaction with sulfamic acid, which forms the internal salt [Me2N=CH0S03] and NH3 to provide both activator and nucleophile. ... 

Substitution. Alcohols ate transformed into secondary and tertiary amines in the Ir-catalyzed reaction with an ammonium salt. Remarkably, the counter-anion of the ammonium salt determines the extent of iV-alkylation. ... 

CycUc alcohols ate excellent targets for enantioselective enzymatic acylations. For example, acylation of (65) with vinyl acetate catalyzed by Upase SAM-II gives the (R),(3)-ester with 95% ee (81). Similarly (66), which is a precursor for seratonin uptake inhibitor, is resolved in a high yield and selectivity with Amano Upase P (82). The prostaglandin synthon (67) is resolved by the same method into the optically pure alcohol in 35% yield (83). 

Typical approximate v values divided by 10 mVkg are 1.00 for water, 0.65 for structural carbohydrates, 0.62 for soluble caibohydrates, 0.75 for structural proteins, 1.53 for hexane, and 1.09 for v etable oils. In cases where the solid volume changes markedly as extraction proceeds, for example, when alcohols ate used to extract water from solids with carbohydrate or protein-based marcs, the saturation line is strongly... 

An alternate explanation of stereocontrol can be derived from Doering and Young s (1950) interpretation of the asymmetric reduction of methyl ketones by optically active aluminum alcohol-ates. It was suggested that steric interference between R—R and CHg—CH3(LX) exceeds that of R —CH3 and R—CH3 (LXI). Therefore, structure (LXI) is the preferred arrangement for re-... 

The resulting dianion, known as an enediolate (ene = double bond, diol = double alcohol, ate = anion), is protonated during work-up to give an a-hydroxyketone as the final product ... 

In this context, we should also mention that, very recently, a series of coumestan analogs 75 were prepared by intramolecular cydization of related 4-(2-hydroxyphenyl)coimiarins 74 (Scheme 33) [130]. The C-O cydization reaction was in this case promoted by copper(II) acetate in the presence of catalytic amounts of Zn(OTf)2, which facilitates the initial electrophilic metalation of Ore C-3 position of the coxunarin by the copper(II) ion with concomitant alcohol-ate coordination. Final C-O reductive elimination gives the coupled tetracyclic products 75. 

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