Interaction of 1-germatranol hydrate with oxalic acid

Polycarboxylic acids are involved in many life processes, along with germatranes exhibiting high biological activity. At the same time, the studies on the reactions of 1-substituted germatranes with polycarboxylic acids appear to be insufficient. On the one hand, compounds of germatranes with substances containing a car boxyl group were reported to be stable in the presence of water. On the other hand, the germatranic cycle of 1-germatranol hydrate in an aqueous medium is acknowledged to be decomposed by D-tartaric acid to bis(µ-tartrato)di(hydroxy)germanate(IV) triethanolammonium form. In this work, the interaction of 1-germatranol hydrate (H₂O·НОGe(OCH₂CH₂)₃N) with oxalic acid (HOC(O)COOH) in water, dimethyl sulphoxide and acetonitrile alcohol was studied. The reaction in an aqueous medium at 20–25 °С quickly leads to the cleavage of the germatrane skeleton followed by the formation of [(C₂O₄)2Ge(OH)₂] ^2- ·H⁺ ·[(HOCH₂CH₂)₃NH]⁺ bis(oxalate-O,O') dihydroxygermanate triethanolammonium. As a result of the topochemical reaction, exposing the reaction residue following evaporation of water at 50 °С in a vacuum of 2 mm Hg for 2 h subsequently leads to the formation of (ROC(O)COOGe(OCH₂CH₂)₃N(R=H) and N(CH₂CH₂O)₃Ge mono- and bis(germatran-1-yl)oxalate), as well as to the reduction of 1-germatranol. Under additional exposure of the reaction mixture in a 2 mm Hg vacuum at 100 °C for 40 min, O[Ge(OCH₂CH2)₃N]₂ bis(germatran-1-yl)oxide and (germatran-1-yl)formate is formed. Following the water dissolution of the reaction mixtures, the resulting compounds undergo another conversion to bis(oxalate-O,O')dihydroxygermanate triethanolammonium and 1-germatranol. Heating a mixture of 1-germatranol hydrate with oxalic acid in a dimethyl sulphoxide and acetonitrile medium along with 1-germatranyl oxalates leads to the formation of a hydrolytic cleavage product of the germatrane skeleton, bis(oxalate-O,O')dihydroxygermanate triethanolammonium, while the boiling of isoamyl alcohol mainly provides for the esterification reaction with a 1-isoamyloxygermatrane yield exceeding 90 %.

1-germatranol hydrate, oxalic acid, bis(oxalate-O, O')dihydroxy germanate triethanolammonium, (germatran-1-yl)oxalate, bis(germatran-1-yl)oxalate, germatran-1-yl)formate, bis(germatran-1-yl)oxide, esterification, cleavage, topochemical reaction

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