RESEARCH ARTICLE

The transposing of isomer yields in the methanolyses of N-substituted quinolinimides by triethylamine

Theodorus van Es^I; Benjamin Staskun^{II, III, *}; Peter Karuso^III

^IDepartment of Biochemistry and Microbiology, Cook College, Rutgers University, New Brunswick, New Jersey, 08903-0232, USA
^IISchool of Chemistry, University of the Witwatersrand, Johannesburg, South Africa
^IIIDepartment of Chemistry and Biomolecular Sciences, Macquarie University, Sydney, NSW, 2109, Australia

ABSTRACT

The effect of triethylamine in transposing the respective yields of the two isomeric esters ensuing from the methanolysis of N-substituted quinolinimides is described and is rationalized with a mechanism.

Keywords: N-Substituted quinolinimides, methyl 2-carbamoyl-3-pyridinecarboxylates, methyl 3-carbamoyl-2-pyridinecarboxylates, benzenesulfonamide derivatives, triethylamine-induced rearrangements, reaction mechanisms

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Acknowledgements

B.S. thanks Professor H.Nevalainen and Professor P .Karuso of the Department of Chemistry and Biomolecular Sciences at Macquarie University for facilitating his stay in the Department, and Dr S.R. Shengule for several preliminary ¹H NMR determinations.

References and Notes

1 Amongothers:(a)A.A.-M.Abdel-Aziz, Eur. J. Med. Chem., 2007, 42(5), 614-626.         [ Links ] (b) M.M. Blanco, G.J. Levin, C.B. Schapira and I.A. Perillo, Heterocycles, 2002, 57(10), 1881-1890.         [ Links ] (c) S.R. Rahalkar and K.S. Nargund, Indian Drugs, 1986, 23(10), 545-548.         [ Links ] (d) P.M. Harrington, Heterocycles, 1993, 35(2), 683-687.         [ Links ] (e) A. Toth and G.Meyer, US 3966726 (1976).         [ Links ] (f) M. Los, US 4921961 (1990) (g) J.         [ Links ]J. Pascavage, US 1984-677647.         [ Links ] (h) J. Kenyon and K. Thaker, J. Chem. Soc., 1957, 2531.         [ Links ] (i) R.L. Jacobs, US 3960877 (1976).         [ Links ] (j) R.A. Barnes and J.C. Godfrey, J. Org. Chem., 1957, 22, 1043-1045;         [ Links ] (k) M.M. Blanco, I.A. Perillo and C.B. Schapira, J. Heterocycl. Chem, 1999, 36(4), 979-984.         [ Links ]

2 A. Bigotto, V. Galasso, F.P. Colonna and G. Distefano, J. Chem. Soc., Perkin Trans. 2, 1978, 1194-1198.         [ Links ]

3 D.M. Dimitrijevic and Z.D.Tadic, J. Serb. Chem. Soc., 1957, 22, 207-216.         [ Links ]

4 Among others: (a) D.M. Dimitrijevic, Z.D. Tadic and R.P. Saper, J. Serb. Chem. Soc.,1957, 22, 201-206.         [ Links ] (b) P.M. Harrington^1d. (c) T. Goto, M. Konno, M. Saito and R. Sato, Bull. Chem. Soc. Jpn., 1989, 62(4), 1205-10.         [ Links ] (d) G.J. Hitchings and J.M. Vernon, J. Chem. Soc. Perkin Trans. 1, 1990, 1757-63.         [ Links ]

5 M.M. Blanco, M.S. Shmidt and I.A. Perillo, Arkivoc, 2005, 12, 195-204.         [ Links ]

6 According to our DFT//B-P86/TZVPP calculations the Mulliken charges and Paboon bond orders in quinolinic anhydride 1 and in N-substituted quinolinimides 5 indicate that: (i) the calculated charges (ab initio) of the two carbonyls are not that different), and (ii) the 3 -methyl ester 9c is more thermodynamically stable than is the isomeric 2-methyl ester 8c. SciFinder presents the predicted ¹³C-NMR data for numerous N-substituted quinolinimides 5, and also for quinolinic anhydride 1, calculated using Advanced Chemistry Development, lnc.(ACD/Labs) Software V9.07, which likewise confirm the relevant two carbonyl charges to be similar.         [ Links ]

7 W.W.K.R. Mederski, M. Baumgarth, M. Germann, D. Kux and T Weitzel, Tetrahedron Lett., 2003, 44(10), 2133-2136.         [ Links ]

8 A. Scozzafava, L. Menabuoni, F. Mincione, F. Briganti, G. Mincione and C.T. Supuran, J. Med. Chem, 1999, 42(14), 2641-2650.         [ Links ]

9 B.C. Jain, B.H. Iyer and P.C. Guha, J. Indian Chem. Soc, 1947, 24, 177-180.         [ Links ]

10 T. van Es, B. Staskun and M.A. Fernandes, J. Chem. Res. Synop., 2007, 373-376.         [ Links ]

Received 7 June 2011
Revised 23 August 2011
Accepted 14 February 2012

Submitted by invitation to celebrate 2011 the International Year of Chemistry'.
* To whom correspondence should be addressed. E-mail: benmina1@bigpond.com.au