Syntheses of a Novel Class of 5/6/5-Heterocycles: Convenient Routes from Aldehydes to Bis(1,3,4-thiadiazolo)-1,3,5-triazinium Halides

European Journal of Organic Chemistry

Volumn , Issue 12, 1998, Pages 2923-2930

  Anders, Ernst ^a   Wermann, Kurt ^a   Wiedel, Bernd ^a   Günther, Wolfgang ^a   Görls, Helmar ^a  

^a FRIEDRICH SCHILLER UNIVERSITY JENA   (Germany)

Author keywords

1 (Haloalkyl)pyridinium halides; Ab initio calculations; Bis(azolyl)alkanes; Cyclization reactions; Synthetic methods; Thia aza heterocycles

Indexed keywords

EID: 0002214267     PISSN: 1434193X     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1099-0690(199812)1998:12<2923::AID-EJOC2923>3.0.CO;2-2     Document Type: Article

References (47)

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4. Without completeness, for recently developed synthetic procedures and for applications compare the following examples: polysulfur/nitrogen heterocycles seem to be useful candidates for optical and electronic switches, e.g. tetrathiafulvalenes and related compounds serve as components in charge-transfer complexes. - [3a] C. F. Marcos, C. Polo, O. A. Rakitin, C. W. Rees, T. Torraba, Angew. Chem. 1997, 109, 283-285; Angew. Chem. Int. Ed Engl. 1997, 36, 281-283. - [3b] S. Nakatsuji, Y.Amano, H. Kawamura, H. Anzai, Liebigs Ann. 1997, 729-732, and references cited therein.
5. Without completeness, for recently developed synthetic procedures and for applications compare the following examples: polysulfur/nitrogen heterocycles seem to be useful candidates for optical and electronic switches, e.g. tetrathiafulvalenes and related compounds serve as components in charge-transfer complexes. - [3a] C. F. Marcos, C. Polo, O. A. Rakitin, C. W. Rees, T. Torraba, Angew. Chem. 1997, 109, 283-285; Angew. Chem. Int. Ed Engl. 1997, 36, 281-283. - [3b] S. Nakatsuji, Y.Amano, H. Kawamura, H. Anzai, Liebigs Ann. 1997, 729-732, and references cited therein.
6. Without completeness, for recently developed synthetic procedures and for applications compare the following examples: polysulfur/nitrogen heterocycles seem to be useful candidates for optical and electronic switches, e.g. tetrathiafulvalenes and related compounds serve as components in charge-transfer complexes. - [3a] C. F. Marcos, C. Polo, O. A. Rakitin, C. W. Rees, T. Torraba, Angew. Chem. 1997, 109, 283-285; Angew. Chem. Int. Ed Engl. 1997, 36, 281-283. - [3b] S. Nakatsuji, Y.Amano, H. Kawamura, H. Anzai, Liebigs Ann. 1997, 729-732, and references cited therein.
7. E. Anders, K. Wermann, B. Wiedel, J.-J. Vanden Eynde, Liebigs Ann. 1997, 745-752.
8. For example see: [5a] J. B. Polya in Comprehensive Heterocyclic Chemistry (Eds.: A. R. Katritzky, C. W. Rees), Pergamon, Oxford 1984, p. 733. - [5b] Comprehensive Heterocyclic Chemistry II (Eds.: A. R. Katritzky, C. W. Rees, E. F. V. Scriven), Pergamon, Oxford 1996, vol. 1. - [5c] E. Lukevits, Khim Gelerosikl. Soedin. 1995, 6, 723-734: Chem. Abstr. 1996, 124, 105358e.
9. For example see: [5a] J. B. Polya in Comprehensive Heterocyclic Chemistry (Eds.: A. R. Katritzky, C. W. Rees), Pergamon, Oxford 1984, p. 733. - [5b] Comprehensive Heterocyclic Chemistry II (Eds.: A. R. Katritzky, C. W. Rees, E. F. V. Scriven), Pergamon, Oxford 1996, vol. 1. - [5c] E. Lukevits, Khim Gelerosikl. Soedin. 1995, 6, 723-734: Chem. Abstr. 1996, 124, 105358e.
10. For example see: [5a] J. B. Polya in Comprehensive Heterocyclic Chemistry (Eds.: A. R. Katritzky, C. W. Rees), Pergamon, Oxford 1984, p. 733. - [5b] Comprehensive Heterocyclic Chemistry II (Eds.: A. R. Katritzky, C. W. Rees, E. F. V. Scriven), Pergamon, Oxford 1996, vol. 1. - [5c] E. Lukevits, Khim Gelerosikl. Soedin. 1995, 6, 723-734: Chem. Abstr. 1996, 124, 105358e.
11. For example see: [5a] J. B. Polya in Comprehensive Heterocyclic Chemistry (Eds.: A. R. Katritzky, C. W. Rees), Pergamon, Oxford 1984, p. 733. - [5b] Comprehensive Heterocyclic Chemistry II (Eds.: A. R. Katritzky, C. W. Rees, E. F. V. Scriven), Pergamon, Oxford 1996, vol. 1. - [5c] E. Lukevits, Khim Gelerosikl. Soedin. 1995, 6, 723-734: Chem. Abstr. 1996, 124, 105358e.
12. For syntheses and applications see: [6a] E. Anders, J. Tropsch, Bull. Soc. Chim. Belg. 1987, 96, 719-720 - [6b] A. Maquestiau, E. Anders, A. Mayence. J.-J. Vanden Eynde, Chem. Ber. 1991, 124, 2013-2017. - [6c] J.-J. Vanden Eynde, A. Mayence, A. Maquestiau, E. Anders, Synth. Commun 1992, 22, 3141-3150. - [6d] J.-J. Vanden Eynde, J. Godin, A. Mayence, A. Maquestiau, E. Anders, Synthesis 1993, 867-869, and references cited therein.
13. For syntheses and applications see: [6a] E. Anders, J. Tropsch, Bull. Soc. Chim. Belg. 1987, 96, 719-720 - [6b] A. Maquestiau, E. Anders, A. Mayence. J.-J. Vanden Eynde, Chem. Ber. 1991, 124, 2013-2017. - [6c] J.-J. Vanden Eynde, A. Mayence, A. Maquestiau, E. Anders, Synth. Commun 1992, 22, 3141-3150. - [6d] J.-J. Vanden Eynde, J. Godin, A. Mayence, A. Maquestiau, E. Anders, Synthesis 1993, 867-869, and references cited therein.
14. For syntheses and applications see: [6a] E. Anders, J. Tropsch, Bull. Soc. Chim. Belg. 1987, 96, 719-720 - [6b] A. Maquestiau, E. Anders, A. Mayence. J.-J. Vanden Eynde, Chem. Ber. 1991, 124, 2013-2017. - [6c] J.-J. Vanden Eynde, A. Mayence, A. Maquestiau, E. Anders, Synth. Commun 1992, 22, 3141-3150. - [6d] J.-J. Vanden Eynde, J. Godin, A. Mayence, A. Maquestiau, E. Anders, Synthesis 1993, 867-869, and references cited therein.
15. For syntheses and applications see: [6a] E. Anders, J. Tropsch, Bull. Soc. Chim. Belg. 1987, 96, 719-720 - [6b] A. Maquestiau, E. Anders, A. Mayence. J.-J. Vanden Eynde, Chem. Ber. 1991, 124, 2013-2017. - [6c] J.-J. Vanden Eynde, A. Mayence, A. Maquestiau, E. Anders, Synth. Commun 1992, 22, 3141-3150. - [6d] J.-J. Vanden Eynde, J. Godin, A. Mayence, A. Maquestiau, E. Anders, Synthesis 1993, 867-869, and references cited therein.
16. [7a] M. Freund, G. Meinecke, Ber. Dtsch. Chem. Ges. 1896, 2511 - 2517. -
17. [7b] Commercially available product: Sigma-Aldrich Chemie GmbH, Steinheim, Germany.
18. G. Werber, F. Buccheri, M. Gentile, J. Heterocycl. Chem. 1977, 14, 1263-1265.
19. L. Antolini, A. Cornia, A. C. Fabretti, W. Malavasi, J. Crystallogr. Spectrosc. Res. 1993, 23, 967-971, and references cited therein.
20. NH2 = -0.912. - [10a] A. E. Reed, L. A. Curtiss, F. Weinhold, Chem. Rev. 1988, 88, 899-926.
21. + = 25.3.
22. For the application of salts 4 for further cyclization reactions cf.: [12a] J.-J. Vanden Eynde, P D'Orazio, A. Maquestiau, E. Anders. Tetrahedron 1992, 48, 1263-1268. [12b] J.-J. Vanden Eynde, A. Mayence, A. Maquestiau, E. Anders, Bull Soc Chim. Belg. 1992, 101, 801-806.
23. For the application of salts 4 for further cyclization reactions cf.: [12a] J.-J. Vanden Eynde, P D'Orazio, A. Maquestiau, E. Anders. Tetrahedron 1992, 48, 1263-1268. [12b] J.-J. Vanden Eynde, A. Mayence, A. Maquestiau, E. Anders, Bull Soc Chim. Belg. 1992, 101, 801-806.
24. Previous routes to geminal bis(pvridmium) salts: [13a] F. Krohnke, H. Leister, Chem Ber. 1958, 91, 1295-1300. - [13b] B. Almarzoqi, A. V. George, N. S. Isaacs, Tetrahedron 1986, 42, 601-607.
25. Previous routes to geminal bis(pvridmium) salts: [13a] F. Krohnke, H. Leister, Chem Ber. 1958, 91, 1295-1300. - [13b] B. Almarzoqi, A. V. George, N. S. Isaacs, Tetrahedron 1986, 42, 601-607.
26. 0], [ab initio values]: N1-C3 130.3(6) [132.1], N1-C1 144.9(7) [146.4], N3-C3 134.3(6) [131.7], N3-C4 132.1(7) [131.7], N5-C4 132.7(6) [132.1]. N5-C1 147.6(6) [146.4], C1-C8 152.3(7) [151.6], N1-N2 139.3(5) [136.4], N2-C2 127.8(6) [126.7], S1-C3 172.8(6) [176.0], S1-C3 172.0(6) [172.2]; N1-C1-N5 106.1(4) [104.1], N1-C1-C8 110.2(4) [112.9], N5-C1-C8 114.5(4) [112.9], C8-C1-H1 114(3) 110.3], N1-C1-H1 109(3) [108.1], N5-C1-H1 103(3) [108.1], C3-N1-C1 123.9(4) [124.9], N1-C3-N3 126.4(5) [125.6], C4-N3-C3 113.5(5) [113.0], N3-C4-N5 124.6(5) [124.2], C4-N5-C1 124.2(4) [124.9], C3-N1-N2 118.0(4) [117.5], N1-C3-S1 108.7(4) [109.3], C3-S1-C2 89.5(3) [88.2], N2-C2-S1 114.6(4) [114.1].
27. [15a] M. J. S. Dewar, E. G. Zoebisch, E. F.Healy, J. J. P. Stewart, J. Am. Chem. Soc. 1985, 107, 3902-3909. -
28. [15b] J. J. P. Stewart, J. Comput. Chem. 1989, 10, 209-220.
29. naphthyl of the conformers at 227 K: -63° and 118.7°.
30. M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binlley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez, J. Q. A. Pople, Gaussian 94, Revision E.1, Gaussian, Inc., Pittsburgh, PA, USA, 1995.
31. T. La Cour, Acta Crystallogr. 1994, B30, 1642-1643.
32. L. Antolino, A. Cornia, A. C. Fabretti, W. Mulavasi, J. Crystallogr. Spectrosc. Res. 1993, 23, 967-971.
33. [20a] These mechanistic alternatives have been investigated by PM3-MO calculations. This method definitely predicts the pathway via 11a to be energetically favoured. -
34. 1 = Ph or Me. An explanation was found on the basis of semiempirical and ab initio calculations.
35. N5 = -0.32 (numbering cf. Figure 2).
36. The reaction conditions have not been optimized for that synthesis.
37. 0], [ab initio values]: N(1)-C(1) 146.1(4) [144.0], N(6)-C(1) 146.9(4) [144.7], N(1)-C(2) 136.6(4) 135.3], N(6)-C(8) 136.4(5) [135.2], N(3)-C(2) 130.2(4) [127.6], N(8)-C(8) 129.7(5) [127.8], N(3)-C(5) 135.6(4) [136.4], N(8)-C(11) 135.7(4) [136.2], N(4)-C(5) 129.6(5) [127.8], N(9)-C(11) 129.7(5) [127.9], N(4)-N(5) 139.2(4) [136.5], N(9)-N(10) 138.4(5) [136.6], N(5)-C(6) 128.8(5) [127.2], N(10)-C(12) 129.4(6) [127.1], N(1)-N(2) 137.9(4) [136.2], N(6)-N(7) 137.4(4) [136.1]. N(7)-C(9) 128.4(5) [126.1], N(2)-C(3) 128.2(4) [126.0]. C(1)-C(14) 151.2(5) [-]; N(1)-C(1)-N(6) 108.1(3) [112.3], N(6)-C(1)-C(14) 113.0(3) [-], N(1)-C(1)-C(14) 112.2(3) [-], C(2)-N(1)-C(1) 124.2(3) [123.9], N(3)-C(2)-N(1) 121.9(3) [121.1], C(2)-N(3)-C(5) 118.5(3) [120.3], N(3)-C(5)-S(2) 119.7(3) [119.4], C(6)-S(2)-C(5) 87.7(2) [86.4], C(7)-C(6)-S(2) 124.3(3) [123.2]. The intensity data for the compounds were collected with an Enraf- Nonius CAD4 diffractometer for 7a and with a Nonius-Kappa CCD for 8a and 8c. The following programs were used: data reduction: MOLEN, DENZO; structure solution: SHELXS; structure refinement: SHELXL-93; structure presentation: SHELXL/PC. Further details of the crystal structure investigations are available on requests from the Fachinformationszentrurn Karlsruhe, Gesellschaft für wissenschaftlichtechnische Information mbH, D-76344 Eggenstein-Leopoldshafen, on quoting the depository numbers CSD-408232 (7a), -408233 (8a), -408234 (8c), the names of the authors, and the journal citation.
38. 13C(160.26, C-5, thiadiazole III/IV).
39. J. R. Cheeseman, G. W. Trucks, A. T. Keith, M. J. Frisch, J Chem. Phys. 1996, 104, 5497-5509. (Basis set: HF/6-31+G*// 6-31+G*. method: NMR = GIAO in Gaussian 94).
40. [26a] E. Diez-Barra, A. de la Hoz, A. Sanchez-Migallon, J. Tejeda, Heterocycles 1992, 34, 1365-1373, and references cited therein. -
41. [26b] Related bis(azolyl)alkanes with 2,3-dihydro-1,3,4-thiadiazole moieties, cf.: K. N. Zelenin, V. A. Khrustalev, V. V.Alekseev, P. A. Sharbatyan, A. T. Lebedev, Chem. Heterocycl. Compd. (Engl. Transl.) 1982, 18, 683-689; Khim. Geterosikl. Soedin 1982, 904-910; D. M. Evans, D. R. Taylor, J. Chem. Soc., Chem. Commun. 1982, 188-189; D. M. Evans, L. Hill, D. R. Taylor, M. Myers, J. Chem. Soc., Perkin Trans. 1 1986, 1499-1506; related imino-bridged 1,3,4-thiadiazoles: C. T. Supuran, Rev. Roum. Chim. 1995, 40, 643-652.
42. [26b] Related bis(azolyl)alkanes with 2,3-dihydro-1,3,4-thiadiazole moieties, cf.: K. N. Zelenin, V. A. Khrustalev, V. V.Alekseev, P. A. Sharbatyan, A. T. Lebedev, Chem. Heterocycl. Compd. (Engl. Transl.) 1982, 18, 683-689; Khim. Geterosikl. Soedin 1982, 904-910; D. M. Evans, D. R. Taylor, J. Chem. Soc., Chem. Commun. 1982, 188-189; D. M. Evans, L. Hill, D. R. Taylor, M. Myers, J. Chem. Soc., Perkin Trans. 1 1986, 1499-1506; related imino-bridged 1,3,4-thiadiazoles: C. T. Supuran, Rev. Roum. Chim. 1995, 40, 643-652.
43. [26b] Related bis(azolyl)alkanes with 2,3-dihydro-1,3,4-thiadiazole moieties, cf.: K. N. Zelenin, V. A. Khrustalev, V. V.Alekseev, P. A. Sharbatyan, A. T. Lebedev, Chem. Heterocycl. Compd. (Engl. Transl.) 1982, 18, 683-689; Khim. Geterosikl. Soedin 1982, 904-910; D. M. Evans, D. R. Taylor, J. Chem. Soc., Chem. Commun. 1982, 188-189; D. M. Evans, L. Hill, D. R. Taylor, M. Myers, J. Chem. Soc., Perkin Trans. 1 1986, 1499-1506; related imino-bridged 1,3,4-thiadiazoles: C. T. Supuran, Rev. Roum. Chim. 1995, 40, 643-652.
44. [26b] Related bis(azolyl)alkanes with 2,3-dihydro-1,3,4-thiadiazole moieties, cf.: K. N. Zelenin, V. A. Khrustalev, V. V.Alekseev, P. A. Sharbatyan, A. T. Lebedev, Chem. Heterocycl. Compd. (Engl. Transl.) 1982, 18, 683-689; Khim. Geterosikl. Soedin 1982, 904-910; D. M. Evans, D. R. Taylor, J. Chem. Soc., Chem. Commun. 1982, 188-189; D. M. Evans, L. Hill, D. R. Taylor, M. Myers, J. Chem. Soc., Perkin Trans. 1 1986, 1499-1506; related imino-bridged 1,3,4-thiadiazoles: C. T. Supuran, Rev. Roum. Chim. 1995, 40, 643-652.
45. [26b] Related bis(azolyl)alkanes with 2,3-dihydro-1,3,4-thiadiazole moieties, cf.: K. N. Zelenin, V. A. Khrustalev, V. V.Alekseev, P. A. Sharbatyan, A. T. Lebedev, Chem. Heterocycl. Compd. (Engl. Transl.) 1982, 18, 683-689; Khim. Geterosikl. Soedin 1982, 904-910; D. M. Evans, D. R. Taylor, J. Chem. Soc., Chem. Commun. 1982, 188-189; D. M. Evans, L. Hill, D. R. Taylor, M. Myers, J. Chem. Soc., Perkin Trans. 1 1986, 1499-1506; related imino-bridged 1,3,4-thiadiazoles: C. T. Supuran, Rev. Roum. Chim. 1995, 40, 643-652.
46. We thank Dr. A. Opitz (Hans-Knöll-Institut für Wirkstoff-Forschung, Jena) for providing us with a sample of that unpublished compound.
47. J.-L. Barascut, R.-M. Claramunt, J. Elguero, Bull. Soc. Chim. Fr. 1973, 1849-1853.