Formose Reactions. II. The Photochemical Formose Reaction

Abstract

Under UV irradiation in the presence of an inorganic base, aqueous formaldehyde was found to give pentaerythritol and 2-hydroxymethylglycerol as the main products, accompanied by the concomitant formation of a mixture of sugars and sugar alcohols. The results indicate that this photochemical formose reaction is considerably different in product distribution from the thermal formose reaction using the Ca(OH)2 catalyst. The detailed examination of the photochemical formose reaction was carried out in the presence of Na2CO3, and a possible scheme for the formation of pentaerythritol and 2-hydroxymethylglycerol is proposed.

The prebiotic synthesis of carbohydrates: A reassessment

“…This behavior does not support previous suggestions that the formose reaction might have been the basis for a selection process, depending upon differing product compositions produced by various minerals (Cairns-Smith et al, 1972). Shigemasa (1977) reported that irradiation of 8 M formaldehyde containing 0.62 M Na2CO 3 produced 2-hydroxymethylglycerol and pentaerythritol as major products. A more recent report (Irie 1989) also describes a highly selective synthesis of ethylene glycol and pentaerythritol via ~-irradiation of dehyde in the presence of 0.05 M K2CO 3 for 10 h and analyzed by GC and HPLC after carrying out a reduction with sodium borohydride.…”

Facula, Faculae

“…2) (Schwartz and de Graaf 1993a). Other nonsugar products have been observed from photochemical formose reactions by others (Shigemasa et al 1977). …”

“…For example, HCHO photochemically reacts to give mostly pentaerythritol (Schwartz and De Graaf 1993), among other nonsugar products ( Fig. 2) (Shigemasa et al 1977). …”

Über die Entstehung von Zuckern und zuckerähnlichen Substanzen aus in Zeolithen absorbiertem Formaldehyd durch UV-Bestrahlung / Synthesis of Sugars and Sugar-Like Products by UV Irradiation of Formaldehyde Absorbed on Zeolites

“…Über die photochemische Umwandlung des Formaldehyds (FA) in Zucker und Zuckeralkohole in wäßrigen Lösungen haben erstmals Moore und Webster [1], später Baly, Heilbron und Barker [2,3] und neuerdings Shigemasa, Matsuda, Sakazawa und Matsuura [4] berichtet. Im Hinblick auf das von Hoyle und Wickramasinghe [5] diskutierte -aber keineswegs überzeugend bewiesene -Vorkommen von Zuckern und Cellulose im interstellaren Raum ist interessant, daß Zucker und zuckerähnliche Stoffe auch durch Einwirkung von y-Strahlen auf FA entstehen, der in Silikatgerüsten, wie sie in Zeolithen vorliegen, absorbiert ist [6].…”