Vargha László et al. (szerk.): Beszámoló a Gyógyszeripari Kutató Intézet 10 éves működéséről 1950-1959 (Budapest, 1969)
Hajós Andor - Fuchs Oszkár: Szintetikus vizsgálatok a klóramfenikollal kapcsolatban
при наличии цианидных ионов, под влиянием хлоралгидрата, из синтетизированного комплекса кальция-бора (LX X) образовался соответствующий комплекс хлорамфеникола (ЪХХ1), из которого путем гидролиза в слабо кислотной среде удалось получить хлорамфеникол (ЪХХП). Образовавшийся в качестве побочного продукта Ds (—)-трео-/3-р-нитрофенилсерин-н-бутиловый эфир рацемизировался уже при нагревании, и таким образом, снова был применен при синтезе. A. HAJÓS, О. FUCHS: STUDIES ON SYNTHESIS OF CHLORAMPHENICOL. Our first attempts at synthesizing chloramphenicol which started from trans-p-nitro-cinnamyl alcohol (XIV) led, instead of it, to the isomeric l-p-nitrophenyl-3- -diehloroacetaminopropane-l,2-diol, since the prepared intermediate erythro-1 -p-nitrophenyl-l-methoxy-2-bromo-propane-3-ol (XX), when fused with potassium phthalimide, converted into a 3-phthalimino compound (XXI). A new preparation method, with the methyl ether of trans-cinnamyl alcohol as starting material, proved successful, as here conversion has not set in. Derivatives of O-methylphenyl serines (XXXIX, LIII), prepared from cis- and tians-einnamylic acid, when reduced, nitrated, demethylated and dichloracetylated, ultimately yielded chloramphenicol. The n-butyl ester of threo-/3-p-nitrophenyl serine was resolved by means of d-camphor sulphonic acid in optical antipodes and the obtained n-butyl ester of Ls( —) -threo-jS-p-nitrophenyl serine reduced with calcium borohydride. The resulting calcium-boro complex (LXX), as aqueous solute, reacted upon chloralhydrate in the presence of cyanide ions and yielded the corresponding chloramphenicol complex (LXXI). Then, from that by weak acid hydrolysis chloramphenicol (LXXII) was made to split off. As by-product of the process n-hutyl ester of Ds(—)-threo-/3-p-nitrophenyl serine was gained, which simply, hy heating rearranged to the racemic compound, to be included anew in the stmthesis. 5 Gyógyszeripari Kutató Intézet 65
