Synlett 2014; 25(08): 1137-1141
DOI: 10.1055/s-0033-1340981
letter
© Georg Thieme Verlag Stuttgart · New York

A Facile and Expeditious One-Pot Synthesis of α-Keto-1,3,4-oxadiazoles

Dalip Kumar*
Department of Chemistry, Birla Institute of Technology and Science, Pilani – 333 031, Rajasthan, India   Fax: +44(113)3436565   eMail: dalipk@pilani.bits-pilani.ac.in
,
Meenakshi Pilania
Department of Chemistry, Birla Institute of Technology and Science, Pilani – 333 031, Rajasthan, India   Fax: +44(113)3436565   eMail: dalipk@pilani.bits-pilani.ac.in
,
V. Arun
Department of Chemistry, Birla Institute of Technology and Science, Pilani – 333 031, Rajasthan, India   Fax: +44(113)3436565   eMail: dalipk@pilani.bits-pilani.ac.in
,
Bhupendra Mishra
Department of Chemistry, Birla Institute of Technology and Science, Pilani – 333 031, Rajasthan, India   Fax: +44(113)3436565   eMail: dalipk@pilani.bits-pilani.ac.in
› Institutsangaben
Weitere Informationen

Publikationsverlauf

Received: 24. Dezember 2013

Accepted after revision: 19. Februar 2014

Publikationsdatum:
24. März 2014 (online)


Abstract

An efficient and high-yielding protocol for the preparation of α-keto-1,3,4-oxadiazoles has been developed. Formation of α-keto-1,3,4-oxadiazoles involves the 2-iodoxybenzoic acid/tetraethylammonium bromide mediated oxidative cyclization of hydrazide-hydrazones generated in situ from the reaction of aryl glyoxal and hydrazides. This one-pot protocol is reasonably general for the preparation of α-keto-1,3,4-oxadiazoles under mild conditions in short reaction times.

 
  • References and Notes

    • 1a Amir M, Shikha K. Eur. J. Med. Chem. 2004; 39: 535
    • 1b Rapolu S, Alla M, Bommena VR, Murthy R, Jain N, Bommareddy VR, Bommineni MR. Eur. J. Med. Chem. 2013; 66: 91
    • 1c de Oliveira CS, Lira BF, Barbosa-Filho JM, Lorenzo JG. F, de Athayde-Filho PF. Molecules 2012; 17: 10192
    • 2a Xie Y, Liu J, Yang P, Shi X, Li J. Tetrahedron 2011; 67: 5369
    • 2b Stabile P, Lamonica A, Ribecai A, Castoldi D, Guercio G, Curcuruto O. Tetrahedron Lett. 2010; 51: 4801
  • 3 Guin S, Ghosh T, Rout SK, Banerjee A, Patel BK. Org. Lett. 2011; 13: 5976
    • 4a Dohi T, Ito M, Yamaoka N, Morimoto K, Fujioka H, Kita Y. Tetrahedron 2009; 65: 10797
    • 4b Zhdankin VV, Stang PJ. Chem. Rev. 2008; 108: 5299
    • 4c Silva JL. F, Olofsson B. Nat. Prod. Rep. 2011; 28: 1722
    • 4d Zhdankin VV. J. Org. Chem. 2011; 76: 1185
    • 4e Kumar D, Arun V, Maruthi Kumar N, Acosta G, Noel B, Shah K. ChemMedChem 2012; 7: 1915
    • 4f Tantak MP, Kumar A, Noel B, Shah K, Kumar D. ChemMedChem 2013; 8: 1468
    • 4g Duschek A, Kirsch SF. Angew. Chem. Int. Ed. 2011; 50: 1524
    • 4h Satam V, Harad A, Rajule R, Pati H. Tetrahedron 2010; 66: 7659
    • 5a Ghosh H, Yella R, Ali AR, Sahoo SK, Patel BK. Tetrahedron Lett. 2009; 50: 2407
    • 5b Singh CB, Ghosh H, Murru S, Patel BK. J. Org. Chem. 2008; 73: 2924
    • 5c Vaddula B, Leazer J, Varma RS. Adv. Synth. Catal. 2012; 354: 986
    • 6a Moriarty RM. J. Org. Chem. 2005; 70: 2893
    • 6b Prabhu G, Sureshbabu VV. Tetrahedron Lett. 2012; 53: 4232
    • 6c Stang PJ, Zhdankin VV. Chem. Rev. 1996; 96: 1123
  • 7 Donohoe TJ, Kabeshov MA, Rathi AH, Smith IE. D. Org. Biomol. Chem. 2012; 10: 1093
  • 8 Moorthy JN, Neogi I. Tetrahedron Lett. 2011; 52: 3868
  • 9 Wagh YS, Tiwari NJ, Bhanage BM. Tetrahedron Lett. 2013; 54: 1290
  • 10 Prabhu G, Sureshbabu VV. Tetrahedron Lett. 2012; 53: 4232
  • 11 Palmer JT, Hirschbein BL, Cheung H, McCarter J, Janc JW, Yu ZW, Wesolowski G. Bioorg. Med. Chem. Lett. 2006; 16: 2909
  • 12 Ohmoto K, Yamamoto T, Okuma M, Horiuchi T, Imanishi H, Odagaki Y, Kawabata K, Sekioka T, Hirota Y, Matsuoka S, Nakai H, Toda M, Cheronis JC, Spruce LW, Gyorkos A, Wieczorek M. J. Med. Chem. 2001; 44: 1268
  • 13 Otrubova K, Boger DL. ACS Chem. Neurosci. 2011; 3: 340
  • 14 Rydzewski RM, Burrill L, Mendonca R, Palmer JT, Rice M, Tahilramani R, Bass KE, Leung L, Gjerstad E, Janc JW, Pan L. J. Med. Chem. 2006; 49: 2953
    • 15a Lu Y, Li C.-M, Wang Z, Ross CR, Chen J, Dalton JT, Li W, Miller DD. J. Med. Chem. 2009; 52: 1701
    • 15b Xiao M, Ahn S, Wang J, Chen J, Miller DD, Dalton JT, Li W. J. Med. Chem. 2013; 56: 3318
  • 16 El Sayed KA. Phytochemistry 2000; 53: 675
  • 17 Kudelko A. Tetrahedron 2011; 67: 8502
  • 18 Zarudnitskii EV, Pervak II, Merkulov AS, Yurchenko AA, Tolmachev AA. Tetrahedron 2008; 64: 10431
  • 19 Cui L, Liu Q, Yu J, Ni C, Yu H. Tetrahedron Lett. 2011; 52: 5530
  • 20 Bellale EV, Bhalerao DS, Akamanchi KG. J. Org. Chem. 2008; 73: 9473
  • 21 One-Pot Synthesis of 4a–m; General Procedure: A mixture of arylglyoxal (1 mmol) and arylhydrazide (1 mmol) was stirred in acetonitrile at r.t. for 3 h. After consumption of the starting materials, IBX (1 mmol) was added to the reaction mixture followed by addition of TEAB (1.2 mmol) and stirring was continued at r.t. for another 3 h. Upon completion of the reaction, solvent was removed in vacuo and the crude material thus obtained was diluted with H2O and extracted with EtOAc (3 × 25 mL). The combined organic layers were washed with saturated NaHCO3 (20 mL), brine (20 mL), and dried over anhydrous Na2SO4. After filtration, the solvent was evaporated under reduced pressure and the residue was recrystallized from ethanol to afford analytically pure α-keto-1,3,4-oxadiazoles 4am in excellent yields. Phenyl(5-phenyl-1,3,4-oxadiazol-2-yl)methanone (4a): Yield: 90%; white solid; mp 143–144 °C (Lit.19 143–145 °C). IR (KBr): 1666, 1535, 1411, 1380, 1280, 1180 cm–1. 1H NMR (400 MHz, DMSO-d 6): δ = 8.45 (dd, J = 8.3, 1.1 Hz, 2 H), 8.15 (dd, J = 8.2, 1.3 Hz, 2 H), 7.74 (t, J = 7.4 Hz, 1 H), 7.64–7.56 (m, 5 H). 13C NMR (101 MHz, DMSO-d 6): δ = 182.13, 170.13, 165.71, 139.76, 139.31, 137.90, 135.60, 134.48, 133.78, 132.43, 127.70. MS (ESI): m/z [M + H]+ calcd for C15H10N2O2: 251.08; found: 251.1. Phenyl(5-p-tolyl-1,3,4-oxadiazol-2-yl)methanone (4b): Yield: 91%; white solid; mp 142–143 °C (Lit.19 139–141 °C). IR (KBr): 1659, 1489, 1450, 1381, 1265, 1173 cm–1. 1H NMR (400 MHz, DMSO-d 6): δ = 8.47 (dd, J = 8.4, 1.2 Hz, 2 H), 8.06–8.04 (m, 2 H), 7.79–7.75 (m, 1 H), 7.65–7.61 (m, 2 H), 7.45 (d, J = 8 Hz, 2 H), 2.46 (s, 3 H). 13C NMR (101 MHz, DMSO-d 6): δ = 176.85, 165.49, 160.26, 143.13, 134.36, 133.64, 130.27, 129.66, 128.39, 127.13, 119.47, 21.17. MS (ESI): m/z [M + H]+ calcd for C16H12N2O2: 265.1; found: 265.2. [5-(4-Methoxyphenyl)-1,3,4-oxadiazol-2-yl]phenyl-methanone (4c): Yield: 91%; white crystalline solid; mp 169.6–170 °C. IR (KBr): 1612, 1574, 1551, 1489, 1380, 1285 cm–1. 1H NMR (500 MHz, DMSO-d 6): δ = 8.41 (d, J = 7.7 Hz, 2 H), 8.10 (d, J = 8.5 Hz, 2 H), 7.81 (t, J = 7.2 Hz, 1 H), 7.68 (t, J = 7.5 Hz, 2 H), 7.23 (d, J = 8.5 Hz, 2 H), 3.89 (s, 3 H). MS (ESI): m/z [M + H]+ calcd for C16H12N2O3: 281.09; found: 281.2.
  • 22 One-Pot Synthesis of 7a–e; General Procedure: A mixture of arylglyoxal (1 mmol) and 2-hydrazinopyridine (1 mmol) was stirred in acetonitrile at r.t. for 5 min. Subsequently, IBX (1 mmol) was added to the reaction mixture, followed by the addition of TEAB (1.2 mmol) in portions. The resulting mixture was stirred at r.t. for 15 min. Upon completion of the reaction, solvent was removed in vacuo, the contents were diluted with H2O, and the mixture was extracted with EtOAc (3 × 25 mL). The combined organic layers were washed with saturated NaHCO3 (20 mL), brine (20 mL), and dried over anhydrous Na2SO4. After filtration, the solvent was removed under reduced pressure and the residue thus obtained was recrystallized from ethanol to afford α-keto-1,2,4-triazolo[4,3-a]pyridines 7ae in excellent yields. (1,2,4-Triazolo[4,3-a]pyridine-3-yl)phenylmethanone (7a): Yield: 90%; light-yellow solid; mp 167 °C. IR (KBr): 1658, 1573, 1496, 1450, 1411, 1380 cm–1. 1H NMR (400 MHz, DMSO-d 6): δ = 9.51 (dd, J = 7.0, 1.0 Hz, 1 H), 8.51 (dd, J = 5.2, 3.3 Hz, 2 H), 8.05 (dd, J = 8.1, 1.0 Hz, 1 H), 7.73–7.67 (m, 2 H), 7.62–7.57 (m, 2 H), 7.32 (t, J = 7.4 Hz, 1 H). MS (ESI): m/z [M + H]+ calcd for C13H10N3O: 224.08; found: 224.2.