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Formation of novel 1,3-thiazole- and 1,2-thiazole-fused aporphines and study on the simultaneously occurring benzothiazole–benzisothiazole-type isomerization

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Abstract

The synthesis and acid-catalyzed rearrangement of novel thiazolomorphinandienes have been presented. An isomerization was observed simultaneously with the backbone transformation. An extensive study was performed to determine the major effects of the isomerization of 2′-alkyl- and aryl-substituted thiazoloapocodeines into 3′-alkyl- and arylisothiazoloapocodeines. The obtained results provided another practical example of the reversible benzisothiazole–benzothiazole-type isomerization emphasizing the determining role of the thermal effects in the occurrence of these isomerization products. The obtained experimental results and the proposed mechanism were in agreement with the calculated DFT data.

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Notes

  1. Provided the fundamental experimental method for the study of photoisomerization. Japanese scientists applied a Riko UVL-100HP (100 W) high-pressure mercury vapour lamp operated at wavelengths between 180 and 420 nm with a peak at 366 nm. Duration of the irradiation was 42 h. It means a total of 4,200 Wh of irradiation. In our photoisomerization studies the same quantity of irradiation was used.

  2. Applied media are commonly used in the pharmaceutical industry for dissolution tests, and their quality is in agreement with pharmaceutical requirements: pH = 1.2—0.1 N hydrochloride solution. pH = 3.0—0.05 M sodium chloride solution adjusted to pH 3.0 with hydrochloride solution. pH = 4.5, 6.8 and 7.4—0.05 M sodium dihydrogen phosphate buffer adjusted to the target pH with sodium hydroxide solution. pH = 10.0—0.05 M ammonium chloride solution adjusted to pH 10.0 with ammonia solution.

  3. The model for thebaine (1) obtained at the B3LYP/6-31G* level was very much in accord with X-ray data (ref.: Mahler CH, Stevens ED, Tundell M-L, Nolan SP (1996) Acta Crystallogr C 52:3193) for compound 1. All computations were performed using a dual-core Intel Xeon 5130 processor at 2.0 GHz. The CPU times for the geometry optimization steps were in the range of 4,812–7,332 s. The total time for geometry steps was 321 h.

  4. See Footnote 2.

  5. See Footnote 1.

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Acknowledgments

The authors are grateful to Prof. Sándor Antus for substantial discussions and to the National Science Foundation (Grant OTKA reg. No. T049436 and NI61336) for the financial support. We thank the Péter Pázmány Programme (NKTH, RET006/2004) for allowing us to use the microwave reactor and to Szabolcs Fekete for the valuable technical help.

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  1. Department of Organic Chemistry, University of Debrecen, P.O. Box 20, 4010, Debrecen, Hungary

    Attila Sipos & Sándor Berényi

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  1. Attila Sipos
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  2. Sándor Berényi
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Correspondence to Attila Sipos.

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Sipos, A., Berényi, S. Formation of novel 1,3-thiazole- and 1,2-thiazole-fused aporphines and study on the simultaneously occurring benzothiazole–benzisothiazole-type isomerization. Monatsh Chem 140, 387–396 (2009). https://doi.org/10.1007/s00706-008-0038-x

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