Über die Konstitution des Sparassols

Abstract

iiche mykocide Wirkungen entfalkk. Niihere Angaben iiber die Physiologie und Biologie dieser Bildungen werden in den aMykol. Untersuchungen und Berichtencc1) demnachst erscheinen. Es zeigte sich, dal3 die Krystalle organischer Natur sind, sich in alkalihalligeni Wasser Iosen, und durch Destillntion mit Wasserdanipf in reineni Zustand nahezu quantitativ aus dein Kultursubstrat gewonnen werden koriiieii. Damit war die Moglichkeit gegeben, geniigende Mengeri zur AufklBrung ihi-er Konstitution rein zu g e w i m n , die Prof. W e d e k i n d z ) fmundlichst iibernommen und gemeinsam mit Priv.-Doz. Dr. F1 e is c h e r durchgefiihrt hat. Sie schlagen fur diesen neuen Korper mit der von ihnen bestimmten Konstitution den Namen sparas as sol^ vor. Im Lnufe der Zeit gelang es, den Gehalt der Rohrcheu an Sparassol soweit anzureichern, da13 aus 100 g Agar-Nahrsubstanz (enthaltend 5 g Malzextra!d und 1.50/,, Agar-Agar) in 8 Monaten 0.1 g Sparassol-Ausheute ziemlicli regelma13ig gewonnen wurde. Das Malzextrakt e n t h d t 33 o/o Wasser, ini wasserfreien Extrakt 64 O/o Maltose (mit F e h 1 i n g scher Losung bestimmt), 0.8 O/" Stickstoff und 42 O//o Kohlenstoff. 2 ) Mit L i e b c r 111 a 11 11 s Reagens gab Sparassol lteine Farhenreaktion, eine Eigenschafl, dic bei p-substituierten Phenolen beobaclitet worden ist (vergl. 11. M e y c r , Konstilutionserniittlung organ. Substanzen, 3. Aufl., S. 483). 3) B e r z i g und W e n z e l , M. 24, 896, 899 [1903]. Beridite d. D. Chem. Gesellschaft. Jahrg. LVI. 165

Structure of the lichen depsidone gangaleoidin

“…This gave methyl 3,5-dichloro-2-( 6-hydroxy-3-methoxycarbonyl-4-methoxy-2-methylphenoxy) -4-methoxy-6-methylbenzoate(8) (50 mg) as prisms (from benzene-cyclohexane), m.p. (1 H, s, ArH), 6.08, 6.11, 6.19, 6.38, and 6.52 (each 3 H, s, OMe), and 7.78 and 7.80 (each 3 H, s, Me); m/e 476 (14%, M+), 475(17), 474(70, M+), 473(26), 472(100, M+), 442( 14), 441 (6), 440 (21) , 406(4), 404(9), 389(7), 382(17), 381(6), 380(24), 263(1), 261(1), 234{2), 232(3), 225(16), 209(15), 193(10), and 165(10).…”

“…Methyl (210 ml) was added dropwise to a stirred solution of the amine (20) (20.8 g) in dichloromethane (670 ml) a t -70 "C. The cooling bath was removed and the mixture was stirred for a further 5 min and then poured into aqueous sodium carbonate. The usual work-up gave the bromo-compound (21) as an oil (28.7 g, 98y0), T 3.50 (1 H, s, ArH), 5.85br ( 2 H , NH,), 6.12 and 6.22 (each3 H, s,OMe),and 7.78 (3 H,s,Me).…”

Two new antifungal metabolites produced by Sparassis crispa in culture and in decayed trees

“…Cwielong, 1986;Hutterman, 1987). The compound, given the trivial name sparassol, was shown to be methyl-2-hydroxy-4-methoxy-6-methylbenzoate (Wedekind & Fleischer, 1923, 1924. In subsequent screenings for antibiotic production, S. crispa has been noted as moderately active (Wilkins & Harris, 1944;Robbins et al, 1945;Hervey, 1947), and suppression of growth of Bacillus subtilis on agar media pre-inoculated with S. crispa has been attributed to sparassol (Siepmann, 1987).…”

Biomimetic syntheses of polyketide aromatics from pyrylium salts

“…B y analogy, it seemed likely that attack of suitable enolate derivatives on pyrylium salts of general structure (22) might generate the interesting selectively protected polyketone system (23). This is based on a standard reaction of simple pyrylium salts, which are known to be susceptible to ring cleavage following attack by certain classes of carbon nucleophile."…”

“…Of particular relevance is the reaction with Wittig reagents, which typically follows the steps illustrated in Scheme 3 leading ultimately to the formation of a new aromatic ring."." B y analogy, it seemed likely that attack of suitable enolate derivatives on pyrylium salts of general structure (22) might generate the interesting selectively protected polyketone system (23). Although two keto groups are now derivatised as enol ethers, rather than one as orginally envisaged in (19), a 2-Alkoxypyrylium salts such as (22) can be considered to be derivatives of an a-pyrone rather than a y-pyrone, and they were inaccessible to early workers because the available alkylating agents were not sufficiently powerful to alkylate the relatively weakly basic a-pyrone carbon yl.…”