O-cholesteryl

The stratum corneum intercellular lipids exist as a continuous lipid phase occupying about 20% of the stratum corneum volume and arranged in multiple lamellar structures. They are composed of cholesterol (27 /o) and ceramides (41 /o), together with free fatty acids (9 /o), cholesteryl esters (10 /o) and cholesteryl sulfate (2 /o) (Table 1). Phospholipids, which dominate in the basal layer, are converted to glucosylceramides and subsequently to ceramides and free fatty acids, and are virtually absent in the outer layers of the stratum corneum. Eight classes of ceramides have been isolated and identified in human stratum corneum but the functions of the individual ceramide types are not fully understood. Similarly, the exact function of cholesterol esters within the stratum corneum lamellae is also elusive but it is theoretically possible that cholesterol esters may span adjacent bilayers and serve as additional stabilizing moieties. 

Figure 4.4.19 Structures of organotin(IV) derivatives containing the O-cholesteryl-O-phenyl phosphoroth-iolate ligand...

Figure 25. Inverse of selective reflection maxima (o=p) as a function of composition for a number of binary chiral nematic mixtures. Here the components are O cholesteryl formate/cholesteryl chloride (at 50 °C), A cholesteryl propionate/cholesteryl chloride (at60°C), cholesteryl heptanoate/cholesteryl chloride (at 60 °C), A cholesteryl laurate/cholesteryl chloride (at 60°C) [105],...

Fig. 3 Effect of cholesteryl ethers in liposomes prepared with DOPC on the relative amount of glucose released (A) (x) cholesterol (o) cholesteryl methyl ether ( ) cholesteryl ethyl ether (v) cholesteryl-n-propyl ether ( ) cholesteryl isopropyl ether (A) cholesteryl butyl ether (B) (x) cholesterol (o) cholesteryl (2 -hydroxy)-3-ethyl ether ( ) cholesteryl methoxy methyl ether ( ) cholesteryl acetate.

Other Elimination Reactions.—The Norrish Type II dealkoxylation reaction of a-alkoxy-ketones is well known.A closely related process has been developed to convert alcohols into alkenes. Thus irradiation of the O-cholesteryl thio-benzoate (191) gave cholesta-3,5-diene (192) in high yield (Scheme 53). 

---