Alcohols, reduction

Metal-ammonia-alcohol reductions of aromatic rings are known as Birch reductions, after the Australian chemist Arthur J Birch who demonstrated their usefulness begin nmg m the 1940s... 

Reduction to Amino Alcohols. Reduction can be brought about using diborane—dimethyl sulfide in THF (80). NaBH in ethanol is also... 

Pervaporation. Vapor arbitrated pervaporation is used to remove ethanol from whiskey by selective passage of the alcohol through a membrane. Whiskey flows on one side of a membrane. A water-vapor stream flows on the other side and sweeps away the ethanol that permeates the membrane. Thus alcohol reduction and selective retention of flavor and aroma components can be achieved usiag membranes with a particular porosity. The ethanol can be recovered by condensing or scmbbiag the vapor stream. Pervaporation systems operate at or slightly above atmospheric pressure (Fig. 

In this process the addition of water vapor to the sweep stream can be controlled so that the water activity of the gas phase equals that of the beverage. When this occurs, there is no transport of water across the membrane. The water content of both the beverage feed and the sweep stream is kept constant. These conditions must be maintained for optimum alcohol reduction. The pervaporation system controls the feed, membrane, airstream moisture level, and ethanol recovery functions. An operational system has been developed (13). 

Table 6. Alcohol Reduction Using Pervaporation Process...

Fig. 6. High pressure reverse osmosis system for alcohol reduction.

Fig. 2. Schematic of alcohol reduction ia beverages. Countercurrent dialysis is combiaed with distillation. The separation process is isothermal, and high boiling iagredients, present ia the dialysate, are preserved. In this fashion, alcohol removal is accompHshed with minimal perturbation ia flavor.

A remarkable feature of the Birch reduction of estradiol 3-methyl ether derivatives, as well as of other metal-ammonia reductions, is the extreme rapidity of reaction. Sodium and -butyl alcohol, a metal-alcohol combination having a comparatively slow rate of reduction, effects the reduction of estradiol 3-methyl ether to the extent of 96% in 5 minutes at —33° lithium also effects complete reduction under the same conditions as is to be expected. Shorter reaction times were not studied. At —70°, reduction with sodium occurs to the extent of 56 % in 5 minutes, although reduction with lithium is virtually complete (96%) in the same time. (The slow rates of reduction of compounds of the 5-methoxytetralin type is exemplified by 5-methoxy-tetralin itself with sodium and f-butyl alcohol reduction occurs to the extent of only 50% in 6 hours vs. 99+% with lithium.) The iron catalyzed reaction of sodium with alcohols must be very fast since it competes so well with the rapid Birch reduction. One cannot compensate for the presence of iron in a Birch reduction mixture containing sodium by adding additional metal to extend the reaction time. The iron catalyzed sodium-alcohol reaction is sufficiently rapid that the aromatic steroid still remains largely unreduced. 

Conversion of Acid Chlorides into Alcohols Reduction Acid chlorides are reduced by LiAJH4 to yield primary alcohols. The reaction is of little practical value, however, because the parent carboxylic acids are generally more readily available and can themselves be reduced by L1AIH4 to yield alcohols. Reduction occurs via a typical nucleophilic acyl substitution mechanism in which a hydride ion (H -) adds to the carbonyl group, yielding a tetrahedral intermediate that expels Cl-. The net effect is a substitution of -Cl by -H to yield an aldehyde, which is then immediately reduced by UAIH4 in a second step to yield the primary alcohol. 

Conversion of Esters into Alcohols Reduction Esters are easily reduced by treatment with L1AIH4 to yield primary alcohols (Section 17.4). 

The most common reactions of carboxylic acid derivatives are substitution by water (hydrolysis) to yield an acid, by an alcohol (alcoholysis) to yield an ester, by an amine (aminolysis) to yield an amide, by hydride ion to yield an alcohol (reduction), and by an organometallic reagent to yield an alcohol (Grignard reaction). 

The mechanisms of most alcohol reductions are obscure. Hydrogenolysis of benzyl alcohols can give inversion or retention of configuration, depending on the catalyst. - ... 

In general, reduction of amides to alcohols is difficult. More commonly the amide is reduced to an amine. An exception uses LiH2NBH3 to give the alcohol. Reduction with sodium metal in propanol also gives the alcohol.Acyl imidazoles are also reduced to the corresponding alcohol with NaBH4 in aqueous HC1. °... 

The alcohol reduction process invented by Hirai and Toshima is widely applicable for the preparation of colloidal precious metals stabilized by organic pol5mers such... 

Noble metal ions can be easily reduced to the corresponding zero-valent metal atoms. Therefore, bimetallic nanoparticles consisting of two different noble metals have been extensively investigated for purpose of novel catalysts and optical materials. A simultaneous reduction of two noble metal ions with alcohol is a simple and useful technique to prepare bimetallic nanoparticles. The alcohol reduction of metal ions M + is followed by Equation (1). 

Our first attempt of a successive reduction method was utilized to PVP-protected Au/Pd bimetallic nanoparticles [125]. An alcohol reduction of Pd ions in the presence of Au nanoparticles did not provide the bimetallic nanoparticles but the mixtures of distinct Au and Pd monometallic nanoparticles, while an alcohol reduction of Au ions in the presence of Pd nanoparticles can provide AuPd bimetallic nanoparticles. Unexpectedly, these bimetallic nanoparticles did not have a core/shell structure, which was obtained from a simultaneous reduction of the corresponding two metal ions. This difference in the structure may be derived from the redox potentials of Pd and Au ions. When Au ions are added in the solution of enough small Pd nanoparticles, some Pd atoms on the particles reduce the Au ions to Au atoms. The oxidized Pd ions are then reduced again by an alcohol to deposit on the particles. This process may form with the particles a cluster-in-cluster structure, and does not produce Pd-core/ Au-shell bimetallic nanoparticles. On the other hand, the formation of PVP-protected Pd-core/Ni-shell bimetallic nanoparticles proceeded by a successive alcohol reduction [126]. 

Recently, Somorjai, Yang et al. [143] examined this reaction over lwt.% Pt/SBA-15 utilizing an elaborate preparation protocol. Preformed Pt nanoparticle sols of five different mean sizes, obtained by alcohol reduction in the presence of a protecting polymer (PVP) were combined with SBA-15 silica exhibiting 9nm pores. After 3h low-power ultrasonic treatment, the Pt particles were evenly distributed throughout the pores of the support (Figure 12 (a)-(e)). 

On the other hand, one of the mildest chemical procedures is an alcohol reduction of metal salts in the presence of the protective agents [4,5]. The reaction proceeds according to the Equation (3). 

This alcohol reduction method is applied to the control of size and composition of not only the noble metal/noble metal [7] but the 3d-transition metal/noble metal nanoparticles [8] like magnetic FePt nanoparticles. 

Alcohol Reduction Reduces hepatic glucose production... 

It is unexpected that the presumably thermodynamically controlled metal in alcohol reduction gives the... 

Allyl halides, reduction reactions, 31 Aluminum chloride reagent/catalyst alkyl halide reduction, 30-31 secondary alkyl alcohol reduction, 14-15... 

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