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To cite this article: Hisao Shibata & Sumio Shimizu (1974) Synthesis of a New Tautomer of
Diosphenol (Buccocamphor), Agricultural and Biological Chemistry, 38:9, 1741-1741, DOI:
10.1080/00021369.1974.10861407
Article views: 56
~
I I
V"O ",,-/,'0 V"OH
I I
A A /"
1 2 3 (Iso-diosphenol)
FIG. 1. Tautomers of Diosphenol. , , , , , , ,
(ii) 7 6 5 4 3 2 I o
We now succeeded in isolating a new taut orner of
diosphenol, 3 accompanied in the course of the synthesis FIG. 2. NMR Spectrum of Iso-diosphenol, 3 (CCh).
of 1. The characteristic signal due to Hs appears at 3.07
(- )-Menthone was oxidized with ferric chloride in ppm (heptet) and there is no methyl signal adjacent to
dioxane according to the method of A. K. Macbeth and C=C bond (1.80 ppm), which is observed in the NMR
W. G. P. Robertson,3) and the resulting dark red oily spectrum of 1. From these facts the structure of the
product was crystallized from methanol. The crystals compound now obtained is concluded as 3-hydroxy-p-
thus obtained have melting point of 82~ 3°C and menth-2-en-2-one, 3.
its structure was confirmed to be 1 by comparing the IR This is the first report dealing with the new tautomer
and NMR spectra with those of the authentic sample. of diosphenol undoubtedly. We propose to name iso-
On the other hand, the filtrate was evaporated to afford diosphenol to this new taut orner, 3.
a red oil, which was chromatographed on silica gel
column with benzene. The eluate gave a pale yellow
REFERENCES
oil, and gas chromatogram of this oil revealed the
presence of two main peaks which attributed to 3 1) "Rodd's Chemistry of Carbon Compounds,"
(tR, 4.5 min) and 1 (tR, 5.5 min); (SE-30--1m, 120°; 2nd Ed., Vol. II B, Elsevier Publishing Co.,
Nz, 1.2 kgjcm2). The ratio of the two components was Amsterdam, 1968, pp. 202.
about 4 (3): 1 (1). This mixture was subjected to the 2) F. W. Semmler and C. E. McKenzie, Ber., 39,
preparative g1c; SE-30 column (1 >; 200 cm), carrier gas 1158 (1906).
(N2, 60 mljmin), and the former component 3 was 3) A. K. Macbeth and W. G. P. Robertson, J. Chern.
Soc., 1953, 3512.
t Studies on the Isomerization of Terpenoids. 4) R. J. W. LeFevre, F. Maramba and R. L. Werner,
Part I. ibid., 1953, 2496.