Synthesis and some transformations of 5-isoxazolylsulfonyl chlorides

P. S. Lebed, A. O. Tolmachov, Yu. O. Zubchuk, O. M. Boyko, M. V. Vovk

Abstract


The effect of the structure of 5-(benzylthio)isoxazoles on selectivity of the synthesis of 5-(chlorosulfonyl)isoxazoles has been determined. The chemical behavior in relation to amines has been described.

Aim. To develop the methods for the synthesis of 5-(chlorosulfonyl)- isoxazoles and 4-chloro-5-(chlorosulfonyl)isoxazoles as promising reagents for construction of prospective bioactive compounds.

Results and discussion. The number of 5-(benzylthio)isoxazoles was obtained by cyclocondensation of N-hydroxyimidoyl chlorides or 2-chloro-2-(hydroxyimino) acetates with benzylethynylsulfide. Their oxidative chlorination with gaseous chlorine led to formation of the mixture of isoxazole-5-sulfonyl chlorides and 4-chloroisoxazole-5-sulfonyl chlorides. The ratio between these products in the mixture depended on the nature of the substitution group in position 3 of the isoxazole ring. For the synthesis of 4-chloro-5-(chlorosulfonyl)isoxazoles with acceptable yields the approach of an advance chlorination of 5-benzylthioisoxazoles by N-chlorosuccinimide with further oxidative chlorination was used.

Experimental part. The synthesis of the starting and target compounds was performed in classic preparative conditions; flesh-chromatography; elemental analysis; LCMS; 1H and 13C NMR-spectroscopy were used.

Conclusions. The reaction of oxidative chlorination of 5-(benzylthio)-3-isoxazoles has been studied. The synthetic approach for the previously unknown representatives of isoxazole-5-sulfonylchlorides has been developed.


Keywords


N-hydroxyimidoyl chlorides; benzylethynyl sulfide; 5-(benzylthio)-3-isoxazoles; oxidative chlorination; isoxazole-5-sulfonylchlorides

Full Text:

PDF

References


Pinho e Melo, T. (2005). Recent advances on the synthesis and reactivity ofisoxazoles. Current Organic Chemistry, 9 (10), 925–958. doi: 10.2174/13852720543684200

Galenko, A. V., Khlebnikov, A. F., Novikov, M. S.et al. (2015). Recent advances in isoxazolechemistry. Russian Chemical Review, 84 (4), 335–377. doi: 10.1070/rcr4503

Hu, F., Szostak, M. (2015). Recent developments in the synthesis and reactivity of isoxazoles: method catalysis and beyond. Advanced Synthesis and Catalysis, 357 (12), 2583–2614. doi: 10.1002/absc.201500319

Manna, K., Banik, U., Grosh, P. S., Dos, M. (2014). A review on synthesis and reactivity of isoxazoles and yrazolines Nirma University Journal of Pharmaceutical Sciences, 1(1), 37–49.

Brunton, L., Chabner, B. A., Knollman, B. (2011). Goodmanand Gilman`s the pharmacological basis of therapeutics. McGrow–Hill.

Lee, C. C., Fitzmaurice, R. J., Caddik, S. (2009). 3,5–Isoxazoles from α–bromopentafluorophenylvinyl sulfonates: synthesis of sulfonates and sulfonamides. Organic and Biomolecular Chemistry, 7 (21), 4349–4351. doi: 10.1039/b911098d

Volkova, Y. A., Averina, E. B., Grishin, Y. K. et al. (2010). Unexpected heterocyclization of electrophilic alkenes by tetranitromethane in the presence of triethylamine. Synthesis of 3–nitroisoxazoles. Journal of Organic Chemistry, 75 (9), 3047–3052. doi: 10.1021/j0100319p

Lahm, G. P., Lett, R. M., Smith, B. T., Smith, B. K. et al. (2010). Nematocidal sulfonamides. Pat. WO 2010129500 (A2); declared 04.05.2009; published 11.10.2010.

Nanyva, Y., Ymai, H., Ida, T., Muratoni, E. et al.(2003). Benzofurylpyrone derivatives. Pat. US 6589984(B1); declared 11.09.2000; published 08.07.2003.

Aertgeerts, K., Breennan, N., Cao, S., Chang, E.et al. (2006). Hydroxysteroid dehydrogenaze inhibitors. Pat. US 20060223829(A1); declared 31.03.2005; published 05.10.2006.

Pulici, M., Zuccoto, F., Badari, A., Nuvoloni, S. et al. (2010). 3,4–Diarylpyrazoles as protein kinase inhibitors. Pat. WO 2010010154(A1); declared 24.07.2008; published 28.01.2010.

Ademri, C., Nesi, R. (1972). Oxidation products of 5–isoxazolthiolsand 5–ethylisoxazoles: sulfoxides, sulfones, sulfonic acids and derivatives. Journal of Heterocyclic Chemistry, 9 (3), 695–697. doi: 10.1002/jhet.5570090336

Zhersh, S., Lukin, O., Matvienko, V., Tolmachev, A. (2010). Synthesis of isomeric fluorobenzene–sulfonyl chlorides. Tetrahedron, 66 (32), 5982–5986. doi: 10.1016/j.tet.2010.06.036

Baker, R. H., Dodson, R. M., Riegel, B. (1946). The cleavage of organic sulfides with chlorine .Journal of the American Chemical Society, 68 (12), 2636–2639.doi: 10.1021/ja01216a063

Barry, W. J., Finar, J. L. (1954). Derivatives of 5–o–merkaptophenyl–3–methyl–1–phenylpyrazole.Journal of the ChemicalSociety, 138–140. doi: 10.1039/jr9540000138

Li, J., Wakefild, B. D., Ruble, J. C. et al. (2007). Preparation of novel antibacterial agents. Replacement of the central aromatic ring with heterocycles. Bioorganic and Medicinal Chemistry Letters, 17 (8), 2347–2350. doi: 10.1016/j.bmcl.2006.12.055

Liu, K–C., Shelton, B. R., Howe, R. K. (1980). A particularly convenient preparation of benzohydroximinoil chlorides (nitrile oxide precursors). Journal of Organic Chemistry, 45 (19), 3916–3918.doi: 10.1021/jo01307a039

Kozikowski, A. P., Adamczyk, M. (1983). Methods for stereoselective cis–cyanohydroxylation and carboxyhydroxylation of olefins. Journal of Organic Chemistry,48 (3), 366–372. doi: 10.1021/jo00151a017

Seidel, W. W., Meel, M. J., Schaffrath, M., Pape, T. (2007). In pursuit of an acetylendithiolate synthesis. European Journal of Organic Chemistry, 2007 (21), 3526–3532. doi: 10.1002/ejoc.200601107


GOST Style Citations


1.         Pinho e Melo, T. Recent advances on the synthesis and reactivity ofisoxazoles / T. Pinho e Melo // Curr. Org. Chem. – 2005. – Vol. 9, Issue 10. – P. 925–958. doi: 10.2174/1385272054368420

2.         Recent advances in isoxazole chemistry / A. V. Galenko, A. F. Khlebnikov, M. S. Novikov et al. // Russ. Chem. Rev. – 2015. – Vol. 84, Issue 4. – P. 335–377. doi: 10.1070/rcr4503

3.         Hu, F. Recent developments in the synthesis and reactivity of isoxazoles : method catalysis and beyond / F. Hu, M. Szostak // Adv. Synth. Catal. – 2015. – Vol. 357, Issue 12. – P. 2583–2614. doi: 10.1002/adsc.201500319

4.         A review on synthesis and reactivity of isoxazoles and pyrazolines / K. Manna, U. Banik, P. S. Grosh, M. Dos //NirmaUniversityJ. Pharm. Sci. – 2014. – Vol. 1, Issue 1. – P. 37–49.

5.        Goodman and Gilman`s the pharmacological basis of therapeutics / eds. L. Brunton, B. A. Chabner, B. Knollman. – McGrow–Hill, 2011.

6.         Lee, C. C. 3,5–Isoxazoles from α–bromopentafluorophenylvinyl sulfonates : synthesis of sulfonates and sulfonamides / C. C. Lee, R. J. Fitzmaurice,S. Caddik// Org. Biomol. Chem. – 2009. – Vol. 7, Issue 21. – P. 4349–4351. doi: 10.1039/b911098d

7.         Unexpected heterocyclization of electrophilic alkenes by tetranitromethane in the presence of triethylamine. Synthesis of 3–nitroisoxazoles / Y. A. Volkova, E. B. Averina, Y. K. Grishin et al. // J. Org. Chem. – 2010. – Vol. 75, Issue 9. – P. 3047–3052. doi: 10.1021/jo100319p

8.        Nematocidal sulfonamides. Pat. WO 2010129500(A2) / Lahm G. P., Lett R. M., Smith B. T., Smith B. K., Tyler C. A. – declared 04.05.2009; published 11.10.2010.

9.         Benzofuryl pyrone derivatives. Pat. US 6589984(B1) / Nanyva Y., Ymai H., Ida T., Muratoni E., Kitaki K., Sugimoto Y., Kosugi T., Takeuchi A., Watanabe K., Tokuyama T., Takeuchi T., Hamada M. – declared 11.09.2000; published 08.07.2003.

10.       Hydroxy steroid dehydrogenaze inhibitors. Pat. US 20060223829(A1) / Aertgeerts K., Breennan N.,Cao S., ChangE., Kiryanova A., Liu X. – declared 31.03.2005; published 05.10.2006.

11.       3,4–Diarylpyrazoles as proteinkinase inhibitors. Pat. WO 2010010154(A1) / Pulici M., Zuccoto F., Badari A., Nuvoloni S., Cervi G., Traqeandi G., Bionrado S., Trifiro P., Marchionni C., Moduguo M. – declared 24.07.2008; published 28.01.2010.

12.       Adembri, G. Oxidation products of 5–isoxazolthiolsand 5–ethylisoxazoles : sulfoxides, sulfones, sulfonicacids and derivatives / C. Ademri, R. Nesi // J. Heterocycl. Chem. – 1972. – Vol. 9, Issue 3. – P. 695–697. doi: 10.1002/jhet.5570090336

13.       Synthesis of isomeric fluorobenzene–sulfonylchlorides /S. Zhersh, O. Lukin, V. Matvienko, A. Tolmachev // Tetrahedron. – 2010. – Vol. 66, Issue 32. – P. 5982–5986. doi: 10.1016/j.tet.2010.06.036

14.       Baker, R. H. The cleavage of organic sulfides with chlorine / R. H. Baker, R. M. Dodson, B. Riegel // J. Am. Chem. Soc. – 1946. – Vol. 68, Issue 12. – P. 2636–2639.doi: 10.1021/ja01216a063

15.       Barry, W. J. Derivatives of 5–o–merkaptophenyl–3–methyl–1–phenylpyrazole / W. J. Barry, J. L. Finar // J. Chem. Soc. – 1954. – P. 138–140.doi: 10.1039/jr9540000138

16.       Preparation of novel antibacterial agents. Replacement of the central aromatic ring with heterocycles / J. Li, B. D. Wakefild, J. C. Ruble et al. // Bioorg. Med. Chem. Lett. – 2007. – Vol. 17, Issue 8. – P. 2347–2350. doi:10.1016/j.bmcl.2006.12.055

17.       Liu, K–C. A particularly convenient preparation of benzohydroximinoil chlorides (nitrile oxide precursors) / K–C. Liu, B. R. Shelton, R. K. Howe // J. Org. Chem. – 1980. – Vol. 45, Issue 19. – P. 3916–3918. doi: 10.1021/jo01307a039

18.       Kozikowski, A. P. Methods for stereoselective cis–cyanohydroxylation and carboxyhydroxylation of olefins / A. P. Kozikowski, M. Adamczyk // J. Org. Chem. – 1983. – Vol. 48, Issue 3. – P. 366–372. doi: 10.1021/jo00151a017

19.       In pursuit of an acetylen dithiolate synthesis / W. W. Seidel, M. J. Meel, M. Schaffrath, T. Pape // Eur. J. Org. Chem. – 2007. – Vol. 2007, Issue 21. – P. 3526–3532. doi: 10.1002/ejoc.200601107





DOI: https://doi.org/10.24959/ophcj.17.922

Abbreviated key title: Ž. org. farm. hìm.

ISSN 2518-1548 (Online), ISSN 2308-8303 (Print)