A structural study of selenobenzamides: Crystal structures and dynamic13C NMR

Chemische Berichte

Volumn 130, Issue 1, 1997, Pages 49-54

  Otten, Pietcr A ^a   Gorter, Syb ^a   Van Gen, Arnc Der ^a  

^a LEIDEN UNIVERSITY   (Netherlands)

Author keywords

4 (p Bromoselenobenzoyl)morpholine; 4 p (Dimethyiamino)selenobenzoyl morpholine; Amides; Hammett treatment; Hindered rotation; Selenium compounds; Selenoamides; Structure elucidation

Indexed keywords

EID: 4043179039     PISSN: 00092940     EISSN: None     Source Type: Journal    
DOI: 10.1002/cber.19971300108     Document Type: Article

References (44)

1. P. A. Otten, A. van der Gen, Reel. Trav. Chim. Pays-Bas 1994, 113, 499. 4-(p-methoxyselenobenzoyl)morphoIine (2c) was prepared in a yield of 73% according to the procedure described in this article.
2. Selenoaldehydes and selenoketones readily oligomerize and/or polymerize:[2a] Polyselenomethylene, see: L. Mortillaro, L. Credali, M. Russo, C. De Chcchi, Polym. Lett. 1965, 3, 581.
3. [2b] 1,3,5-Triselenanes as starting materials for free selenoaldehydes, see: Y. Takikawa, H. Watanabe, M. Asanuma, K. Shimada, Tetrahedron Lett. 1989, 30, 6047.
4. [2c] Dimer of Selenobenzophenone, see: G. Erker, R. Hock, C. Krueger, S. Werner, F.-G. Klärner, U. Artschwaeer-Perl, Angew. cTiem. Int. Ed. Engl. 1989, 29, 1067.
5. [2d] Prepared in situ, selenoaldehydes and selenoketones can be trapped in a hétéro Diels-AIder reaction, see: G. A. Kraft, P. T. Meinke, J. Ain. Chem. Soc. 1986, 705, 1314.
6. [2e] K. Okuma, J. Sakata, Y. Tachibana, T. Honda, Tetrahedron Lett. 1987, 28, 6649.
7. [2f] P. T. Meinke, G. A. Krafft, J. T. Spencer, Tetrahedron Lett. 1987, 28, 3887.
8. [2g] G. Erker, R. Hock, R. Nolle, J. Am. Chem. Soc. 1988, 770, 624.
9. [h] M. Seei, T. Nakajima, S. Suca, J. Am. Chem. Soc. 1988, 770, 1976.
10. [2i] P. T. Meinke, G. A. Krafft, J. Am. Chem. Soc. 1988, 770, 8671.
11. [2j] K. Seci, T. Koyama, T. Nakajima, S. Suga, S. Murai, N. Sonoda, Teïmliedron Lett. 1989, 30, 2095.
12. [2k] R. Hock, S. Hillenbrand, G. Erker, C. Krueger, S. Werner, Chem. Ber. 1993, 726, 1895.
13. [2l] Selenoaldehydes and selenoketones are kinetically stabilized by bulky substituents, see: T. G. Back, D. H. R. Barton, M. R. Britten-Kelly, F. S. Guziec Jr., J. Chem. Soc., Perkin Trans. 7 1976, 2079.
14. [2m] F. S. Guziec Jr., C. A. Moustakis, J. Org. Chem. 1984, 49, 189.
15. [2n] A. Ishi, R. Okazaki, N. Inampto, Bull. Chem. Soc. Jpn. 1988, 61, 861.
16. [2o] R. Okazaki, N. Kumon, N. Inamoto, J. Am. Chem. Soc. 1989, 111, 5949.
17. 0, gave only mediocre linear correlations.
18. 2-) substituents, see: S. Behrendt, R. Borsdorf, E. Kleinpeter, D. Gruendel, A. Hantschmann, Z. Chem. 1976, 16, 405.
19. 2 group are found at a lower field than those of the anti-CH2 group, see: I. D. Rae, Austr. J. Chem. 1979, 32, 567.
20. rot.
21. F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A. G. Orpen, R. Taylor, J. Chem. Soc., Perkin Trans. 2 1987, S1.
22. [8a] R. P. shibaeva, L. O. Atovmyan, Zh. Strukt. Kliim. 1968, 9, 90.
23. [8b] W. Walter, S. Harto, J. Voss, Ada Crystallogr. 1976, B32, 2876.
24. [9a] 5a, see: P. R. Brooks, J. A. Counter, R. Bishop, E. R. T. Tiekink, Ada Cryst. 1991, C47, 1939.
25. [9b] 5b, see: K. Okuma, K. Kojima, I. Kaneko, Y. Tsujimoto, H. Ohta, Y. Yokomori, J. Chem. Soc., Perkin Trans. 1 1994, 2151.
26. [9c] 5c, see: H. Hope, Acta Cryst. 1965, 18, 259.
27. [9d] 5d, see: H. G. Raubenheimer, G. J. Kruger, L. Linford, C. F. Marais, R. Otte, J. T. Z. Hattingh, A. Lombard, J. Chem. Soc., Dalton Trans. 1989, 1565.
28. [9e] 5e, see: H. Fischer, J. Hofmann, U. Gerbing, A. Triliomis, J. Organomet. Chem. 1988, 358, 229.
29. [9f] 5e, see: H. Fischer, A. Triliomis, U. Gerbinc, B. Huber, G. Mueller, J. Chem. Soc., Chem. Commun. 1987, 559.
30. [9g] 5f and 5g, see: H. Fischer, U. Gerbing, A. Triliomis, G. Mueller, B. Huber, J. Riede, J. Hofmann, P. Burger, Chem. Ber. 1988, 121, 2095.
31. Metal complexes in which a selenoaldehyde is η2-cordinated to a metal center show a relatively long C=Se bond, of about 1.9 Å.
32. 2-(PhCH=Se)-\V(CO)5) /(C=Se) = 1.864(1) Å, see: H. Fischer, S. Zeuner, J. Riede, Angew. Chem. Int. Engl. Ed. 1984, 23, 726.
33. [10b] H. Fischer, S. Zeuner, U. Gerbing, J. Riede, C. Kreiter, J. Organomet. Chem. 1989, 577, 105.
34. 2Cp, rf(C=Se) = 1.900(1) A, see: W. A. Herrmann, J. Weichmann, R. Serrano, K. Blechschmitt, H. Pfïsterer, M. Ziegler, Angew. Chem. Int. Ed. Engl. 1983, 22, 314.
35. 2-[Me(H)C=Se]-Rh[(/-Pr)3P],Cp, d(C=Se) = 1.917(5) A, see: H. Werner, L. Hofmann, J. Wolf, G. Mueller, J. Organomet. Chem. 1985, 250, C55.
36. 2-(PhCH=Se)-WCO(;-BuOCH)2, /(C=Se) = 1.961(6) A, see: H. Fischer, U. Gerbing, G. Mueller and H. G. Alt, Chem. Ber. 1987, 720, 1905. Thèse complexes are sometimes referred to as metalla-selena-cyclopropanes, because the C=Se bond has considerable, single-bond character. The average C-Se single bond is 1.97 A, see réf.191. The lengthening of the C=Se bond is a result of donation of electron density from the low-valent metal centers [(W(O), Mn(I) and Rh(I)] into the vacant, low-energy, antibonding norbital of the C=Se bond, see réf.[8].
37. rot of thioamides see: [11a] J. Sandström, J. Phys. Chem. 1967, 71, 2318.
38. [11b] W. Walter, E. Schaumann, Chem. Ber. 1971, 104, 3361.
39. [11cl R. F. Hobson, L. W. Reeves, K. N. Shaw, J. Phys. Chem. 1973, 77, 1228.
40. [11d] R. C. Neumann, Jr., V. Jonas, J. Org. Chem. 1974, 39, 929.
41. H. C. Brown, Y. Okamoto, J. Am. Chem. Soc. 1985, 80, 4979.
42. S. Collins, T. G. Back, A. Rauk, J. Am. Chem. Soc. 1985, 107, 6589.
43. C. Piccinni-Leopardi, O. Fabre, D. Zimmermann, J. Reisse, Can. J. Chem. 1977, 55, 2649.
44. M. L. Martin, J.-J. Delpuech, G. J. Martin, Practical NMR Spectroscopy, Heyden and Sons Ltd., Philadelphia, 1980, p. 445-446.