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Reactivities Involved in The Seliwanoff Reaction: Letter
Reactivities Involved in The Seliwanoff Reaction: Letter
Letter
Reactivities Involved in the Seliwanoff Reaction
Francisco Sánchez-Viesca*, Reina Gómez
Organic Chemistry Department, Faculty of Chemistry, National Autonomous University of Mexico, Mexico City (CDMX), México
Email address:
*
Corresponding author
Received: January 2, 2018; Accepted: January 10, 2018; Published: January 23, 2018
Abstract: The Seliwanoff Reaction, a well-known colour reaction for ketoses, is based in the fact that ketoses are dehydrated
more rapidly than aldoses to give a furfural derivative. Further condensation with resorcinol in dilute hydrochloric acid gives the
colour product. But a problem has remained unsolved for many years: why the ketoses are dehydrated faster than aldoses? Based
on recent experimental results, as well as in ab initio methodology on the chemistry of aldoses and ketoses, we studied the
reactivities involved in dehydrations and isomerizations of these compounds and propose an explanation of why ketose require
less reaction time in the Seliwanoff Test.
Keywords: Aldoses, Especial Reactivities, Ketoses, Reaction Mechanisms, Reactive Intermediates
Finally, acid catalyzed cyclization and dehydration gives β-unsaturated compound and the third water loss affords
furfural. Figure 4. furfural [21]. An example with xylose is in Figure 6.
the hemiketal, and the intermediate enol rearranges to the fact that ketoses react faster than the aldoses in the Seliwanoff
aldehyde. The second dehydration gives the α, β-unsaturated Test, prompted us to direct our attention to the HMF formation
derivative. A third water loss affords hydroxymethylfurfural in order to clear-up the theoretical core that permits an
[25], Figure 8. explanation of the reaction rates involved in the formation of
the key intermediate.
We reviewed the actual information regarding the formation
of furfural and hydroxymethylfurfural from aldopentoses,
aldohexoses and ketohexoses. The isomerization of glucose to
fructose was also revised. All this has been detailed in the
previous section.
If we look at the reactivities involved from fructose to
hydroxymethylfurfural we observe that dehydration is
initiated by protonation of the more reactive OH, the anomeric,
which can be stabilized by resonance, previously to vicinal
deprotonation. Then a tautomerism occurs and two simple
dehydrations of a tetrahydrofuran derivative yield
hydroxymethylfurfural. The first dehydration can be
visualized as an α, β-conjugation but also, prior to
tautomerism, as a very rapid dehydration of the allylic OH,
supported by the enolic electron donation.
On the contrary, in glucose to 5-hydroxymethylfurfural, the
starting protonation does not occur at the most basic OH but at
O-2. Then a cationic rearrangement contraction provides the
Figure 8. Dehydration steps from fructose to HMF. five-member ring intermediate. Two further dehydrations
afford HMF. In this route we observe two not common
The route of glucose to 5-hydroxymethylfurfural has been reactivities, the starting point and the ring contraction.
studied recently using high-level ab initio methods (G4MP2 The isomerization of glucose to fructose, another route to
along with SMD solvation model), [26]. The reaction HMF, also presents an uncommon reactivity, a hydride shift.
mechanism confirms the previous one described for pentoses Besides, the total course implies more steps to HMF and
to furfural, such as xylose [21], i.e., protonation at O-2, water obviously more reaction time.
elimination, ring contraction, neutralization, deprotonation, ― Thus, in the Seliwanoff’s Test ketoses react via a diverse
and two more dehydrations. reaction mechanism than aldoses, being significative
Other ab initio study using density functional and two-layer differences at molecular level.
ONIOM calculations found that no dehydration pathway of ― Fructose presents common reactivities in the synthesis of
open-chain glucose is favoured over its isomerization to hydroxymethylfurfural, this not being the case with glucose or
β-glucopyranose or to fructose. The chair conformers are glucose isomerization to fructose. This explains the different
given in the ring contraction mechanism to reaction times observed in the test and it’s utility for ketose
5-hydroxymethylfurfural [27], Figure 9. identification. Slower reactions resulted in accord with less
common reaction steps, i.e., with especial reactivities.
― The theory of the Seliwanoff’s Reaction has been
cleared-up. This is important because generally aldehydes
react faster than ketones but now we are not dealing with
isolated functional groups but with polyfunctional molecules
with mixed groups.
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