Alcohol discussed

Aromatic alcohols (derivatives of carblnol HCHjOH) may be prepared (compare AltpAaltc Alcohols, discussion preceding Section 111,14) ... 

Summary of Reactions of Alcohols Discussed in Earlier Chapters... 

Many members of this series are known based on nitroparaffin condensations with aldehydes of longer chain length than formaldehyde. However, only the five primary amino alcohols discussed in the following are manufactured on a commercially significant scale. N-Substituted derivatives of these compounds also have been prepared, but only 2-dimethylamino-2-methy1-1-propanol has been available in commercial quantities (Table 1). 

These are generally oxidised with the same kinetics as saturated alcohols but more rapidly. In addition to the example of allyl alcohol - discussed previously (p. 377), several reports exist of oxidations of benzylic alcohols. The importance of a 1 1 complex K = 0.8 0.2 at 25 °C, [HCIO4] = 0.525 M) in the Ce(IV) oxidation is clear from agreement of spectroscopic and kinetic data . For a... 

The third group of target molecules comprises chiral carboxylic acid and their derivatives esters, amides and nitriles. Enantiomerically pure esters are prepared in an analogous manner to the enantiomerically pure alcohols discussed earlier [i.e. by esterase- or lipase-catalyzed hydrolysis or (trans)esterification]. However, these reactions are not very interesting in the present context of cascade reactions. Amides can be produced by enantioselective ammoniolysis of esters or even the... 

The polymerization of an epoxide by hydroxide or alkoxide ion is often carried out in the presence of an alcohol. Why How is the degree of polymerization affected by alcohol Discuss how the presence of alcohol affects both the polymerization rate and molecular weight distribution. 

In comparison with the araliphatic alcohols discussed in Section 2.5.2, very few phenol alcohols are used as fragrance and flavor materials. Neither the alcohols corresponding to vanillin, ethylvanillin, and heliotropin nor their esters have special organoleptic properties. Anise alcohol and its acetate are the only products that are used to some extent in perfume and aroma compositions. 

Besides the l-(but-3-enyl)allyl alcohols discussed above, 2- and 3-(pent-4-enyl)allyl alcohols also undergo clean photobicyclization in the presence of copper trifluoromethanesulfonate as catalyst. However, no intramolecular photocycloaddition product could be isolated from irradiation of a homologous 2-(hex-5-enyl)allyl alcohol.8... 

It has been reported that reaction of n. 3-unsatu rated carboxylic acids with bis(collidine)bromine(l) hexafluorophos-phate leads to the formation of 2-oxetanones in moderate yields (Equation 33) <1999JOC81>. As with the related reaction of cinnamyl alcohols (discussed in Section 2.05.9.1), this 4- electrophilic intermediate. The cyclization reaction was diastereospecific single (E)- or (Z)-isomers were reacted to give single stereoisomeric products. Lactonization was favored by substrates that were /3-dialkyl-substituted, or ct-alkyl/aryl-, /3-aryl-substituted on the C-C double bond. ct-Monoalkyl/aryl, /3-unsubstituted substrates gave either polymeric products or exclusive vinyl bromide formation. 

The chemoselective oxidation of a primary alcohol in the presence of a secondary alcohol is a somewhat more difficult task. Not only is the inherent difference in reactivity less than in the case of the selective oxidation of allylic alcohols discussed above, but most reagents will oxidize secondary alcohols somewhat more rapidly than primary alcohols. Nevertheless there are reagents which will carry out the selective oxidation of a primary alcohol to an aldehyde without oxidizing a secondary alcohol, some of which will be considered here. 

L. R. O. Storey. Proc. Phys. Soc. London) 65B, 943-50 (1952). Melting point, ultrasonic absorption H20-ethanol, 0-25 G C1-C4 alcohols discussed. 

PREPARATION OF ALKYL HALIDES 1. From alcohols. Discussed in Secs. 16.4-16.5. 

PREPARATION OF CARBOXYLIC AODS 1. Oxidation of primary alcohols. Discussed in Sec. 16.8. 

Unlike the majority of alcohols discussed in the two preceding Sections, phenols are relatively inert to phosgene even at elevated temperatures [1080]. Yields of the products can be increased, however if a stoicheiometric equivalent of an organic base is used in the reaction [294,846,1358], or if controlled amounts of alkaline solution are added to the reactants in a suitable solvent [36b,1568]. The effect of tertiary amine in the promotion of... 

The simple amino alcohols discussed have been used as catalysts for enantioselective addition of zinc alkyls to carbonyl compounds (Section D. 1.3.1.4.). In most cases, the reactive amino function is used for the formation of derivatives (including hcterocycles. such as dihydrooxa-zoles. which are formed with acids) which are useful as sources of chiral carbanions (see Sections C., D.l.1.1.2., D.l.3.1.4., D.l.6.1.2.1.. D.1.6.1.3., D.1.6.1.5., D.2.1. and D.2.3.I.). 

Isomeric to the amino alcohols discussed so far are the 2-amino-3-bornanols 43. The exo,exoamino alcohol was obtained from camphorquinone via an imine of 3-e.vo-hydroxycamphor in several steps and used in the synthesis of a./i-unsaturated dihydroxazoles used as chiral dieno-philes41 (Section D. 1.6.1.1.1.2.2.1.1.). 

---