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Synlett 2014; 25(13): 1839-1842
DOI: 10.1055/s-0034-1378277
letter
© Georg Thieme Verlag Stuttgart · New York

An Efficient One-Pot Synthesis of 1,4-Oxathiane and 1,4-Thiomorpholine Derivatives

Alireza Samzadeh-Kermani*
Chemistry Department, Faculty of Science, University of Zabol, Zabol, Iran   Fax: +98(61)335856   eMail: drsamzadeh@gmail.com
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Publikationsverlauf

Received: 26. März 2014

Accepted after revision: 10. Mai 2014

Publikationsdatum:
25. Juni 2014 (online)

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Abstract

An efficient one-pot reaction of nitromethane, isothiocyanates, and three-membered heterocyclic rings (oxiranes and aziridines) for the synthesis of 1,4-oxathiane and 1,4-thiomorpholine derivatives is reported. This procedure is carried out in the presence of K2CO3 in DMF at 60 °C.

Key words

cyclization - epoxides - heterocycles - multicomponent reaction - ring opening

Supporting Information

    for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083.
  • Supporting Information
 

  • References and Notes

  • 1 Janvier P, Sun X, Bienayme H, Zhu J. J. Am. Chem. Soc. 2002; 124: 2550
    Suche in Google Scholar
  • 2 Wess G, Urmann M, Sickenberger B. Angew. Chem. Int. Ed. 2001; 40: 3341
    CrossrefSuche in Google Scholar
  • 3 Cook MJ In Comprehensive Heterocyclic Chemistry . Katrizky AR, Rees CW. Pergamon Press; Oxford: 1984: 3
    Suche in Google Scholar
  • 4 Miyauchi H, Tanio T, Ohashi N. Bioorg. Med. Chem. Lett. 1996; 6: 2377
    CrossrefSuche in Google Scholar
  • 5 Piergentili A, Quaglia W, Giannella M. Bioorg. Med. Chem. 2007; 15: 886
    CrossrefSuche in Google Scholar
  • 6 Ozdemir A, Zitouni G. Turk. J. Chem. 2008; 32: 529
    Suche in Google Scholar
  • 7 Kim JW, Park HB, Chung BY. Bull. Korean Chem. Soc. 2006; 27: 1164
    CrossrefSuche in Google Scholar
  • 8 Haynes RK. Artemisinins: Remarkable Antimalarial Drugs, Current Usages and Problems, and Design of New Derivatives. Workshop Advanced Design and Development of Potential Drugs Against Malaria. ICS UNIDO; Italy: 2009. March
    Suche in Google Scholar
  • 9 Abadi AH, Hegazy GH. Bioorg. Med. Chem. 2005; 13: 5759
    CrossrefSuche in Google Scholar
  • 10 Ollevier T, Lavie-Coupin G. Tetrahedron Lett. 2004; 45: 49
    CrossrefSuche in Google Scholar
  • 11 Yudin AK. Aziridines and Epoxides in Organic Synthesis. Wiley-VCH; Weinheim: 2006
    CrossrefSuche in Google Scholar
  • 12 Brunel JM, Legrand O, Reymond S, Buono G. Angew. Chem. Int. Ed. 2000; 39: 2554
    CrossrefSuche in Google Scholar
  • 13 Reymond S, Legrand O, Brunel JM, Buono G. Eur. J. Org. Chem. 2001; 2819
  • 14 Zhang R, Yu W, Lai TS, Che CM. Chem. Commun. 1999; 409
  • 15 Jing-Yu W, Zhi-Bin L, Li-Xin D, Xue-Long H. J. Org. Chem. 2008; 73: 9137
    CrossrefPubMedSuche in Google Scholar
  • 16 Nozaki K, Nakano K, Hiyama T. J. Am. Chem. Soc. 1999; 121: 11008
    CrossrefSuche in Google Scholar
  • 17 Samzadeh-Kermani A. Monatsh Chem. 2014; 145: 611
    CrossrefSuche in Google Scholar
  • 18 Yavari I, Ghazanfarpour-Darjani M, Hossaini Z, Sabbaghan M, Hosseini N. Synlett 2008; 889
    Thieme Connect
  • 19 Hossaini Z, Rostami-Charati F, Seyfi S, Ghambarian M. Chin. Chem. Lett. 2013; 24: 376
    CrossrefSuche in Google Scholar
  • 20 Ando T, Kano D, Minakata S, Ryu N, Komatsu M. Tetrahedron 1998; 54: 13485
    CrossrefSuche in Google Scholar
  • 21 Typical Procedure for the Preparation of Aryl Hydrazides 5a–l and 6a,b To a stirred mixture of 2 (1.0 mmol), 3, or 4 (1.2 mmol) and K2CO3 (1mmol) in DMF (2 mL), nitromethane (1 mmol, 0.061 g) was added over 30 min, and the mixture was stirred for 8 h at 60 °C. After completion of the reaction (monitored by TLC), the mixture was allowed to cool to r.t., poured into H2O (4 mL), and extracted with CH2Cl2 (3 × 3 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered, and concentrated under vacuum. Finally, the residue was purified by column chromatography to afford pure product.
  • 22 N-Ts-aziridines 4a and 4b were prepared following literature procedures.20 Representative Analytical Data N-(6-methyl-1,4-oxathian-3-ylidene)benzenamine (5a) Pale yellow oil; yield 0.17 g (82%). IR (KBr): νmax = 3025, 2967, 1530, 1330, 1323, 1113 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 1.27 (3 H, d, 3 J = 7.4 Hz, Me), 3.46–3.55 (2 H, m, CH2), 4.63–4.67 (H, m, CH), 4.86 (H, d, 2 J = 10.1 Hz, CH), 4.89 (H, d, 2 J = 10.2 Hz, CH), 7.10 (2 H, d, 3 J = 6.9 Hz), 7.19 (H, t, 3 J = 7.1 Hz), 7.27 (2 H, d, 3 J = 6.7 Hz). 13C NMR (125.7 MHz, CDCl3): δ = 13.6 (Me), 35.3 (CH2), 69.3 (CH), 74.7 (CH2), 118.7 (2 CH), 125.2 (CH), 130.1 (2 CH), 147.8 (C), 165.4 (C). MS: m/z (%) = 207 (2) [M+], 175 (37), 130 (45), 118 (52), 98 (71), 77 (100). Anal. Calcd for C11H13NOS (207.29): C, 63.74, H, 6.32, N, 6.76, S, 15.47. Found: C, 63. 85, H, 6.38, N, 6.55, S, 15.40. 2-[-5-(Phenylimino)-1,4-oxathian-2-yl]phenol (5b) Yellow solid, mp 81–83 °C; yield 0.17 g (58%). IR (KBr): νmax = 3034, 2961, 1551, 1348, 1324, 1130 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 3.46–3.51 (2 H, m, CH2), 4.64–4.68 (H, m, CH), 4.83 (H, d, 2 J = 9.8 Hz, CH), 4.91 (H, d, 2 J = 9.7 Hz, CH), 4.82 (H, br, OH), 6.71–6.78 (2 H, m), 7.02–7.06 (2 H, m), 7.09 (2 H, d, 3 J = 7.4 Hz), 7.22–7.30 (3 H, m). 13C NMR (125.7 MHz, CDCl3): δ = 35.4 (CH2), 69.4 (CH2), 80.2 (CH), 118.6 (CH), 121.2 (CH), 123.2 (2 CH), 125.2 (C), 127.6 (CH), 128.1 (CH), 130.2 (CH), 131.4 (2 CH), 147.4 (C), 153.9 (C), 164.1 (C). MS: m/z (%) = 285 (1) [M+], 208 (17), 192 (53), 152 (65), 134 (79), 107 (100), 77 (63). Anal. Calcd for C16H15NO2S (285.36): C, 67.34, H, 5.30, N, 4.91, S, 11.24. Found: C, 67.52, H, 5.43, N, 4.75, S, 11.16. N-(5-Phenyl-4-tosylthiomorpholin-2-ylidene)benzenamine (6a) Pale yellow solid, mp 89–91.5 °C; yield 0.34 g (80%). IR (KBr): νmax = 3012, 2941, 1555, 1521, 1345, 1324, 1108 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 2.26 (3 H, s, Me), 3.40–3.46 (2 H, m, CH2), 4.23–4.26 (H, m, CH), 4.40 (H, d, 2 J = 11.0 Hz, CH), 4.51 (H, d, 2 J = 11.0 Hz, CH), 7.11–7.34 (10 H, m), 7.39 (2 H, d, 3 J = 6.7 Hz), 7.81 (2 H, d, 3 J = 6.5 Hz). 13C NMR (125.7 MHz, CDCl3): δ = 24.3 (Me), 35.2 (CH2), 50.1 (CH2), 56.4 (CH), 122.4 (2 CH), 127.1 (CH), 127.3 (2 CH), 127.7 (CH), 128.1 (2 CH), 128.8 (2 CH), 129.5 (2 CH), 131.1 (2 CH), 136.3 (C), 139.4 (C), 141.3 (C), 148.7 (C), 164.5 (C). MS: m/z (%) = 422 (1) [M+], 390 (26), 272 (45), 169 (63), 118 (51), 103 (74), 91 (100), 77 (86). Anal. Calcd for C23H22N2O2S2 (422.56): C, 65.37; H, 5.25, N, 6.63, S, 15.18. Found: C, 65.53; H, 5.39, N, 6.81, S, 15.07. N-(5-Benzyl-4-tosylthiomorpholin-2-ylidene)benzenamine (6b) Pale yellow solid, mp 94–96 °C; yield 0.40 g (91%). IR (KBr): νmax = 3012, 2941, 1555, 1521, 1324, 1108 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 2.25 (3 H, s, Me), 2.64 (H, dd, 2 J = 11.6 Hz, 3 J = 6.3 Hz, CH), 2.78 (H, dd, 2 J = 11.6 Hz, 3 J = 6.5 Hz, CH), 3.38–3.49 (2 H, m, CH2), 4.20–4.24 (H, m, CH), 4.38 (H, d, 2 J = 10.8 Hz, CH), 4.43 (H, d, 2 J = 10.8 Hz, CH), 7.11–7.33 (10 H, m), 7.41 (2 H, d, 3 J = 6.6 Hz), 7.83 (2 H, d, 3 J = 6.2 Hz). 13C NMR (125.7 MHz, CDCl3): δ = 24.6 (Me), 34.7 (CH2), 40.2 (CH2), 51.3 (CH2), 57.6 (CH), 121.8 (2 CH), 126.4 (CH), 127.1 (2 CH), 127.3 (CH), 128.3 (2 CH), 128.6 (2 CH), 129.4 (2 CH), 130.6 (2 CH), 135.7 (C), 137.1 (C), 140.5 (C), 149.4 (C), 164.0 (C). MS: m/z (%) = 436 (2) [M+], 404 (24), 286 (36), 155 (65), 131 (51), 118 (79), 91 (83), 77 (100). Anal. Calcd for C24H24N2O2S2 (436.59): C, 66.02; H, 5.54, N, 6.42, S, 14.69. Found: C, 66.25; H, 5.67, N, 6.58, S, 14.57.