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Constitution and Synthesis of an aci-Reductone Formed on Non-oxidative Degradation of Dehydroascorbic Acid.

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are precipitated, which are sucked off, washed with ether,
and dried. The compound can be recrystallized from toluene
under nitrogen.
Received: July 3, 1968
[Z 827 1El
German version: Angew. Chem. 80, 705 (1968)
I"] Dr. P. W. Jolly and Dr. K. Jonas
Max-Planck-Institut fur Kohlenforschung
433 Mulheim-Ruhr, Kaiser-Wilhelm-Platz (Germany)
[ l ] A . D. Allen and C . V . Senoff, Chem. Commun. 1965, 621;
F. Bottomley and S. C . Nyburg, ibid. 1966, 89; A. D . Allen,
F. Bottomley, R. 0.Harris, V. P . Reinsalu, and C . V. Senoff, J.
Amer. chem. SOC.89, 5595 (1967); D. E. Harrison and H. Taube,
ibid. 89, 5706 (1967); A . E. Shilov, A . K . Shi/ova, and Y. G . Borod'ko, Kinetika i Kataliz 7, 768 (1966); Chem. Abstr. 65, 19655b
(1966); D . E . Harrison, E. Weissberger, and H . Taube, Science
(Washington) 159, 320 (1968); A . Yarnamota, S. Kitazume, and
S . Ikeda, J . Amer. chem. SOC.90, 1089 (1968).
[2] A . D. Allen and J . R. Sfevens, Chem. Commun. 1967, 1147.
[ 3 ] A. Sacco and M . Rossi, Chem. Commun. 1967, 313; A . Yamamoto, S . Kitazume, L . S. Pu, and S . Ikeda, ibid. 1967, 79;
A . Yamamoto, L. S . Pu, S . Kitazume, and S . Ikeda, J. Amer.
chem. SOC.89, 3071 (1967); A . Misono, Y. Uchida, T. Saito, and
K. M . Song, Chem. Commun. 1967, 419; A . Misono, U . Uchida,
and T. Saito, Bull. chem. SOC.Japan 40,700 (1967); J . H . Enemark, 8. R. Davis, J . A . McCinnety, and J. A. Ibers, Chem.
Commun. 1968, 96.
[4] J. P. Collman and J. W. Kang, J. Amer. chem. SOC.88, 3459
(1966); J . P. Collman, M . Kubota, Y. Sun, and F. Vastine, ibid.
89, 169 (1967).
[5] K . Jonas, Dissertation, Universitat Bochum, 1968.
[6] C . Kruger, unpublished work.
On use of I-14C-labeled (2) autoradiography of the chromatogram shows that the new compound n o longer contains
C-1; apparently the acid ( 5 ) is decarboxylated slowly even
at room temperature. Polarography of the eluted zone
indicates an enediol grouping and an aldehyde group
activated by conjugation. Kdiss for sulfite addition was
determined, also polarographically, as 1.1x 10-3. The IR
spectrum contains a sharp absorption band at 1700 cm-1;
compounds of tetronediol type, such as ( I ) , (3). 3.4-dihydroxy-2,5-dihydrofuranone, and the corresponding deuterated compounds, however, show two sharp bands, one
between 1630 and 1665 cm-1 and the other between 1737 and
1754cm-l.AtpH5 thecompound gave a UVband withhma,=
291 nm, similar to that of triosereductone (Amax= 288 nm).
From these results it is concluded that decomposition of (2)
leads by way of (5) and (6) to ( 7 ) ; and this has been prepared
also from L-arabinose by way of the osazone and osone c6.71.
Constitution and Synthesis of an aci-Reductone
Formed on Non-oxidative Degradation of
Dehydroascorbic Acid[**]
Enolization of the arabosone t o give (7) occurs analogously
the proton-catalyzed isomerization of hydroxypyruvaldeBy K. Wisser, W . Heimann, and E. Mogelr*1
hyde to triosereductone [a].
The ~-2,3,4,5-tetrahydroxy-2-pentenal
prepared from L-araOn two-electron oxidation L(+)-ascorbic acid ( 1 ) (vitamin C)
binose is chromatographically, polarographically, and UVis converted into L(+)-dehydroascorbic acid (2), which can
and IR-spectroscopically identical with the non-oxidative
be reduced back to ( I ) in vivo and in vitro. The dehydro acid
degradation product of (2).
(2) decomposes non-oxidatively and non-enzymically to
Substance (71, which was obtained in rng quantities. is a
products that are of interest in food chemistry because they
yellow syrup and decomposes slowly at room temperature
cause discoloration and changes in taste.
with browning. We suggest that it be called L-pentosereducCOz, oxalic acid, threonic acid, furfuryl alcohol, ~-xylosone
(?), ethylglyoxal, and 2-keto-3-deoxy-~-pentono-y-lactone tone or erythroreductone.
The aci-reductone formed on warming (2) in dilute sulfuric
(5-hydroxymethyltetrahydro-2,3-furandione)have been deacid is not compound (3)aspreviouslypostulated [ I ] ; authentic
tected as degradation products 11-51. Little is reliably known
(3) has different UV and IR spectra. The product isolated by
about the course of the degradation. A strongly reducing
the procedure of reference is mainly an as yet unidentified
compound arising o n degradation of (2) has been formulated
reducing compound plus a smaller amount of (7).
as (3) f l l but also as (4)[3J.
[Z 828 IEI
Received: May 9, 1968. Expanded: J u n e 7, 1968
German version: Angew. Chem. 80, 755 (1968)
Developing a thin-layer chromatogram of an aqueous solution of (2) obtained o n silica gel or aluminum oxide a t room
temperature affords many zones that obviously arise from
products formed by catalytic decomposition of (2) on silica
gel or aluminum oxide but have been held by most authors
t o represent the initial stage of the degradation of (2). 2.3Diketogulonic acid (5) (RF = 0.1) is obtained after about 1 h
at room temperature on thin-layer chromatography on
cellulose with butanol/glacial acetic acidlwater (4:l :l); after
some weeks a new substance of RF = 0.8 appears which is
strongly reducing analogous to ( I ) . This second zone
appears homogeneous in several eluants and o n two-dimensional thin-layer chromatography.
7 32
[*I Dr. K. Wisser, Prof. Dr.-Ing. W. Heimann, and E. Mogel
Institut fur Lebensmittelchernie der Universitat
75 Karlsruhe, Kaiserstr. 12 (Germany)
[*'I We thank the Bundeswirtschaftsministerium and the Forschungskreis der Ernahrungsindustrie e.V. for financial support
of this work.
[l] H . v . Euler and B. Eistert: Chemie und Biochemie der Reduktone und Reduktonate. F. Enke, Stuttgart 1957, pp. 223-237.
121 B. Drevon, C . Nofre, and A. Cier, C. R. hebd. Seances Acad.
Sci. 243, 607 (1956).
[3] C . Nofre, A . Cier, and B. Drevon, Bull. SOC.chim. France 27,
245 (1960).
[4] D . Nomura and T . Uehaba, Hakko-Kogaku Zasshi (J. Ferment. Technol.) 36, 290 (1958).
[5] T. Kurata, H. Wakabayashi, and Y. Sakurai, Agric. biol.
Chem. (Tokyo) 31, 101, 170, 177 (1967).
[6] W . T . Haskins, R . M . Mann, and C . S. Hudson, J. Amer.
chem. SOC.68, 1766 (1946).
[7] S. G . Bayne, G . A . Collie, and J . A. Fewster, J. chem. SOC.
(London) 1952, 2766.
[8] See [I], p. 45.
Angew. Chem. internnt. Edit.
Vol. 7 (1968)
/ No. 9
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acid, constitutions, synthesis, degradation, reductone, dehydroascorbic, oxidative, non, former, aci
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