3006
M. W. Justik / Tetrahedron Letters 48 (2007) 3003–3007
Scheme 9.
3. Higgins, S. D.; Thomas, C. B. J. Chem. Soc., Perkin Trans.
1 1982, 235–242.
4. Yamauchi, T.; Nakao, K.; Fujii, K. J. Chem. Soc., Perkin
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Santamaria, A. Toxicol. Lett. 1998, 99, 1–13; For lead:
Godwin, H. A. Curr. Opin. Chem. Biol. 2001, 5, 223–227.
6. Yamauchi, T.; Hattori, K.; Nakao, K.; Tamaki, K. J. Org.
Chem. 1988, 53, 4858–4859.
contaminants from the reaction mixture. Recovery of 4
is typically ꢀ90%. Coupled with the yield of reoxidation
(93%) the recycling rate of this material compares favor-
ably with that observed for poly[4-(diacetoxyiodo)sty-
rene].10a Recovery of the reduced poly(4-iodostyrene)
was 80% and a diminishment of the amount of iodinated
sites that could be reoxidised (64 vs 74%) was reported.
7. (a) Justik, M. W.; Koser, G. F. Molecules 2005, 10, 217–
225; (b) Justik, M. W.; Koser, G. F. Tetrahedron Lett.
2004, 45, 6159–6163.
8. Prakash, O.; Goyal, S.; Moriatry, R. M.; Khosrowshahi,
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6, 392–393.
3. Conclusion
In conclusion, we wish to report the conversion of aryl-
alkanones to 2-arylesters with HMBI, a cyclic analog of
HTIB, by oxidative rearrangement. The use of toxic
metal salts or reagents whose reduced by-products inter-
fere with facile purification of the product are avoided.
Once more, the reagent is easily recovered from the reac-
tion mixture, and reoxidized for reuse at high efficiency.
11. Recent articles include: (a) Koposov, A. Y.; Litvinov, D.
N.; Zhdankin, V. V.; Ferguson, M. J.; McDonald, R.;
Tykwinski, R. R. Eur. J. Org. Chem. 2006, 21, 4791–4795;
(b) Koposov, A. Y.; Nemykin, V. N.; Zhdankin, V. V.
New J. Chem. 2005, 29, 998–1000; (c) Zhdankin, V.;
Goncharenko, R. N.; Litvinov, D. N.; Koposov, A. Y.
ARKIVOC 2005, 4, 8–18; (d) Meprathu, B. V.; Justik, M.
W.; Protasiewicz, J. D. Tetrahedron Lett. 2005, 46, 5187–
5190; (e) Koposov, A. Y.; Litvinov, D. N.; Zhdankin, V.
V. Tetrahedron Lett. 2004, 45, 2719–2721.
Acknowledgments
We thank Penn State Erie, The Behrend College for
financial support through new faculty start-up funds.
The Bruker Avance 400 MHz NMR Spectrometer used
in this work was made possible by gifts from the Tho-
mas Lord Charitable Trust and The Orris C. Hirtzel
and Beatrice Dewey Hirtzel Memorial Foundation.
12. Koser, G. F.; Sun, G.; Porter, C. W.; Youngs, W. J. J.
Org. Chem. 1993, 58, 7310–7312.
13. 1H-1-Hydroxy-5-methyl-1,2,3-benziodoxathiole
3,3-di-
oxide (3, HMBI) from 4; procedure adapted from Ref.
12; Peroxyacetic acid (35%, 58 mL) was added dropwise to
a stirred mixture of sodium 2-iodo-5-methylbenzenesulf-
onate (25.40 g, 75.0 mmol) in AcOH (60 mL) and conc.
H2SO4 (10 mL) maintained at 10–15 ꢁC. The mixture was
stirred at this temperature for 1 hour and overnight at rt.
The solid component was isolated by vacuum filtration
and washed with Et2OÆH2O was added to a mixture of this
material in boiling MeCN (300 mL) until the solid had
mostly dissolved. The mixture was filtered hot and allowed
to cool to room temperature. HMBI separated as a
colorless crystalline solid and was isolated by filtration.
The filtrate was concentrated to one third its volume and a
second crop of crystals was obtained. Combined yield of
HMBI: 22.03 g (94%); mp and 1H NMR spectrum
identical with material prepared by Ref. 12.
References and notes
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14. Methyl phenylacetate: Acetophenone (117 lL, 1.00 mmol)
was added to a stirred solution of MeOH (4.0 mL),
TMOF (250 lL) and H2SO4 (213 lL). Crystalline HMBI
(346 mg, 1.10 mmol) was added at once and the resulting