D -rib0 -2 -Be nza mid o -1 ,3,4t r i hydro xy o c ta d e c a n e (Nbe nzo y I -C 1 8p h y to s p h i n g o s i n e) a n d D -rib0 -2be n za mi do -1.3.4-trihydroxyeicosane (N-benzoyl-C20-phytosphingosine) have been synthesised by Wittig reactions between the aldehyde (IX) derived from 2-amino-2-deoxy-13-glucose and the appropriate long-chain phosphoranes. The properties of the derivatives of the synthetic C18-phytosphingosine are identical with those of the corresponding derivatives of the natural base, thus confirming the structure established by previous degradative studies.IN 1911, Zellner described the isolation of a nitrogencontaining substance (" fungus cerebrin ") from the mushroom Amanita muscaria, and later similar materials 2-5 were isolated from other mushrooms, yeasts, and moulds. Reindel and his co-workers3 and Bohonos and Peterson 4 concluded that yeast cerebrin was an amide formed from 4-amino-l,3,5-trihydroxyeicosane (" cerebrin base ") and a fatty acid, and it was shown that cerebrin base gave a crystalline N-benzoyl derivative and a crystalline derivative (" acetone compound 'I), containing acetone, when recrystallised from this solvent. However, Oda reinvestigated the structure of cerebrin base and concluded that it was 2-amino-lJ3,4-trihydroxyoctadecane. Carter and his co-workers reported the presence of a base, with the same structure as that proposed by Oda, in the lipids of plant seeds, and this base gave an "acetone compound" and an N-benzoyl derivative with properties similar to those reported for the corresponding derivatives of cerebrin 1
328ChemInform Abstract The racemic myo-inositol (Ia) is converted by a known procedure to a mixture of the bis-isopropylidene derivatives (Ib)-(Id) which are isolated as benzoates (IVa)-(IVc). In contrast to (IVb) and (IVc), a pure sample of (IVa) cannot be obtained and therefore a pure sample of its parent compound (Ib) is synthesized via the allyl ether (IVd). The allyl ethers (IVd)-(IVf) obtained from (Ib)-(Id) are separated and each is transformed to the respective di-O-allyl-myo-inositol (V). Kinetic acetonation of (Vb) gives the compound (VII). The desired pure (Ib) is then obtained from (IVd) (yield given in mg) by removing the allyl groups by isomerization and subsequent removal of the propen-1-yl groups formed using HgO/HgCl2. -Crystals of the diacetate (IX), obtained from (Vc) as outlined in the scheme (no yield given), show interesting 'jumping' behavior on heating and cooling.
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