CAPÍTULO 6: PARTE EXPERIMENTAL
6.1.10. Complexo tris(3-p-nitrobenzoilamidopicolinato-N-óxido)diaquo gadolínio (III) (27b)
Inicialmente, fez-se o refluxo de Gd(ClO4) 3.4 x 10-2 M (1/3 eq, 0.034 mmol, 0.95 mL) com a base N-N-diisopropilettilamina (1 eq, 0.02 mL) em MeOH (10 mL). Em seguida, adicionou-se, gota a gota, uma solução metanólica do ácido 7b (31.3 mg, 0.11 mmol). O sistema manteve-se em pH 6.0. Decorridas 18 horas resfriou-se a reação e depois filtrou-a. O produto obtido possui aparência de um pó (22.6 mg, 61 %), p.d. 242°C; IV (KBr) 3440, ,3107, 1699,1654, 1523, 1349, 1218 cm-1.
ANEXO
Folha de rosto do trabalho submetido para publicação em maio de 2000 no Journal of Organic Chemistry.
Conformational Studies on 1,2- and 1,2,3-Substituted Heterocycles. A
Spectroscopic and Theoretical Study of 3-Acylaminopicolinic Acid
Derivatives and their N-Oxides
Ivoneide de C. L. Barrosb, Claudia C. C. Bejana, João Bosco P. da Silva*a,
F. W. Joachim Demnitz*a, Hans-Ulrich Gremlichc
a
Departamento de Química Fundamental, Universidade Federal de Pernambuco, Cidade Universitária, 50.670-901 Recife-PE, Brazil, FAX: +55 81 271 8442, E-mail: paraiso@npd.ufpe.br, jdemnitz@npd.ufpe.br; b Departamento de Química, Universidade Federal do Amazonas, Manaus-AM, Brazil; c Novartis Pharma AG, WSJ-503.1001, Lichtstrasse, CH-4002 Basel, Switzerland
Abstract. Theoretical studies involving minimization of model 3-propanoylaminopicolinic acids (10d-
trans, 10d-cis), -methyl ester (10a) and corresponding -N-oxide derivatives (10b, 10c-trans, 10c-cis) using AM1 gave conformations contrary to both sound chemical intuition and experimental data. RHF ab
initio calculations using the 6-31G and 6-31G** basis sets on the other hand corroborated spectroscopic
data. 3-Dodecanoylaminopicolinic acid derivatives (7a-9a, 7b-9b, 7c-9c, 9d) were prepared and studied by NMR and IR spectroscopy. The results show that a strong intramolecular hydrogen bond between amide-H and the 2-carboxyl substituent results in a planar molecular conformation. This is particularly profound in the 3-acylaminopicolinic acid-N-oxides. When the 2-substituent is a methyl ester on the other hand, repulsion between N-oxide and ester functions induces twisting of the carbomethoxy group out of the plane of the aromatic ring. The spectroscopic results were corroborated by RHF ab initio calculations using the 6-13 G basis set. The method used in molecular modeling can have profound impact on the final theoretical result in the case of the abovementioned class of compounds.
REFERÊNCIAS
1. N. Sabbatini, A. Mecati, M. Guardigli, V. Balzani, J. –M. Lehn, R. Zeissel and R.
Ungaro, Lanthanide luminescence in supramolecular species, J. Luminescence,
1991, 48 & 49, 463-468.
2. J. –M. Lehn, Angew. Chem., Int. Ed. Engl, 1990, 29, 1304.
3. L. C. Thompson, Handbook on the Phys. And Chem. Of Rare Earth, Vol. 3, North-
Holland, Amsterdam, 1979, 201.
4. M. J. Weber, Handbook on the Phys. And Chem. Of Rare Earth, ed. K. Gschneidner
and L. Eyring, Amsterdam, 1979, ch. 35.
5. J. –C. G. Bünzli, Lanthanoid Probes in Life, Chemical and Earth Sciences, Theory
and Practice, ed. G. R. Choppin and J. C. Bunzli, Elsevier, Amsterdam, 1989, ch. 7. 6. J. –C. G. Bünzli and J. –M. Pfeffarlé, Helv. Chim. Acta, 1994, 77, 323.
7. G. F. de Sá, L.H. Nunes, Z. –M. Wang and G. R. Choppin, Synthesis,
Characterization, Spectroscopic and Photophysical Studies of Ternary Complexes of Eu(III) with 3-aminopyrazine-2-carboxykic acid (HL) and Heterobiaryl ligands (2,2’-bipyridine and 1,10-phenanthroline), J. Alloys Comp, 1993, 196, 17-23. 8. B. Alpha, R. Ballardini, V. Balzani, J. –M. Lehn, S. Perathoner and N. Sabbatini,
Photoch. And Photobiology, 1990, 52 (2), 299.
9. B. Dietrich, J. –M. Lehn and J. P. Sauvage, Tetrahedron, 1973, 29, 1647.
10. B. Alpha, R. Ballardini, V. Balzani, J. –M. Lehn, S. Perathoner and N. Sabbatini,
Angew. Chem., Int. Ed. Engl, 1987, 26, 266.
11. G. F. de Sá, F. R. G. e Silva and O. L. Malta, J. Alloys Comp., 1994, 457, 207-208.
12. A.V. M. de Andrade, R. L. Longo, A. M. Simas and G. F. de Sá, j. Chem.
13. M. E. Mesquita, Complexos de Lantanídeos com Aminopiridina Carboxilatos como
Novos Precursores na Obtenção de Eficientes Conversores de energia, Tese de
Doutorado em Química, Departamento de Química fundamental-UFPE, Recife,
1997.
14. M. E. Mesquita, G. F. de Sá and F.W.J. Demnitz, J. Alloys Comp., 1998, 275-277,
844-847.
15. I. Hemmilä, J. Alloys Comp.,1995, 225, 480-485; J. Yuan, K. Matsumoto, H.
Kimura, Anal. Chem., 1998, 70, 569-601.
16. R. A. Abramovitch, Pyridine and its Derivatives, Heterocyclic Compounds, John
Willey & Sons, 1974, 14(2), ch 1.
17. E. C. White, Science,1940, 92, 127.; E. C. White and J. H. Hill, J. Bact.,1943, 45,
433.
18. Clemo and McIlwain, J.,1938, 479.; Clemo and Daglish, J.,1950, 1481.
19. Dutcher and Wintersteiner, J. Biol. Chem.,1944, 155, 359.
20. Robinson, Chem. And Ind., 1925, 44, 456.
21. E. P. Linton, J. Amer. Chem. Soc., 1940, 62, 1945.
22. E. Ochiai, J. Org. Chem., 1953, 18,534.
23. R. A. Barnes, A comparasion of the Structure and Reactivity of Pyridine and
Pyridine-1-oxide, J. Org. Chem., 1959, 81, 1935.
24. C. M. Bax.m A. R. Katritzky and L. E. Sutton, J. Chem. Soc., 1958, 1258.
25. M. Liveris and J. Miller, J. Chem. Soc.,1963, 3486.
26. J. C. Morrow, D. Ulka and B. P. Huddle, American Crystallographic Association,
Winter Meeting Abstracts, March, 1970.; Chem. Abstr., 1971, 74, 147553w.
27. A. Musumeci, R. P. Bonomo, V. Cucinotta and A. Seminara, Lanthanide
28. A. N. Speca, L. I. Pytlewski, N. M. Karayannis and C. Owens, J. Inorg.
Chem.,1974, 36, 3751.
29. D. K. Koppikar, P. V. Sivapullaiah, L. Ramakrishnan and S. Soundararajan,
Structure and Bonding, 1978, 34, 135.; A. Musumeci, R. P. Bonomo and A.
Seminara, Chim. Acta, 1980, 45, L169.
30. S. A. Boyd, R. E. Kohrman and O. X. West, Inorg. Nucl. Chem. Lett., 1976, 49, 15.
31. S. P. Sinha, Complexes of the Rare Earths, 1966, Pergamon Press, 5 ed., ch. 4, 66.
32. M. E. Mesquita, G. F. de Sá, M. A. B. Lopes, O. L. Malta, Synthesis,
Characterization and Photophysical Studies of the Europium(III) Complex with 3- Aminopyridine-2-carboxylic Acid, J. Chem. Res., 1996, 120.
33. G. F. de Sá, B. B. Neto and R. Ferreira, 2-Pyrazinecarboxylic acid Complexes of
Lanthanide Ions, Inorg. Chim. Acta, 1977, 23, 249-252. 34. J. Albertsson, Acta Chem. Scand., 1970, 24, 1213.
35. E. Hansson, Acta Chem. Scand., 1970, 24, 2969.
36. Ahrland, Chatt and Davies, Quart. Ver.,1958, 12, 265.
37. Ho, T.-L. Hard and Soft Acids and Bases Principle in Organic Chemistry,
Academic press, New York, 1977.
38. D. F. Shriver, P. W. Atkins, C. H. Landford, Inorganic Chemistry, 2 ed., 1994, p.
239.
39. S. P. Sinha, Complexes of the Rare Earths, Pergamon Press, 1966, ch. 1, 11.
40. S. P. Sinha, Chimika Chronika,1983, 29A, 223.
41. W. C. Martin, R. Zalubas and L. Hagan, Atomic Energy Levels the Rare Earth
Elements, NSRDS-NBS 60, National Bureau of Standards, Washington, DC, 1978. 42. G. H. Dieke, Spectra and Energy Level of Rare Earth Ions in Crystals, Interscience,
43. K. Binnemans, C. G.-Walrand, Chem. Phys. Letters, 1995, 235, 163-174.
44. S. P. Sinha, Europium, New YorK, 1967.
45. R. D. Shannon, Acta Cryst., 1976, A32, 751-767.
46. G. Blasse and L. H. Brixner, X-Ray-excited Luminescence of Organic Gadolinium
Compounds, 1990, 109, 172-175.
47. G. F. Buono-Core and H. Li, Quenching of Excited States by Lanthanide Ions and
Chelates in Solution, Coord. Chem. Rev., 1990, 55.
48. L. Prodi, M. Maestri, R. Ziessel and V. Balzani, Inorg. Chem.,1991, 30 3798.
49. V.-M. Mukkala, M. Kwiatkowski, Angew. Chem., ed. Engl., 1993, 76, 893.
50. S. I. Weissman, J. Chem. Phys., 1942, 10, 214.
51. G. A. Crosby, R. E. Whan, R. M. Aline, J. Chem. Phys., 1961, 34, 743.
52. Y. Matsuda, S. Makishima and S. Shinoya, Bull. Chem. Soc. Jpn., 1968, 41, 1513..
53. W. M. Watson, R. P. Zerger, J. T. Yardley and G. D. Stucky, Inorg. Chem., 1975,
14, 2675.
54. W. R. Dawson, J. I. Kropp and M. W. Windsor, J. Chem. Phys., 1966, 45, 2410; M.
Tanaka, G. Yamaguchi, J. Shokawa and C. Yamanaka, Bull. Chem. Soc. Jpn.,1970, 43, 549; S. Sato and M. Wada, Bull. Chem. Soc. Jpn.,1970, 43, 1955; ª V. Hayes and H. G. Drickamer, J. Chem. Phys., 1982, 76, 114.
55. G. A. Crosby, R. E. Whan and J. J. Freeman, J. Chem. Phys., 1962, 66, 2493
56. W. Kiggen, F. Vögtle, Angew. Chem., 1984, 96, 712; W. Kiggen, F. Vögtle, S.
Franken and H. Puff, Tetrahedron,1986, 42, 1856.
57. L.B. McGown, Analitical Chemistry, 1989, 61, 14.
58. Freeman and Crosby, J. Phys. Chem.,1963, 67, 2717.
60. a)N. Filipescu, W. F. Sager and F. A. Serafin, Substituent Effects on Intramolecular
Energy Transfer. II. Fluorescence Spectra of Europium and Terbium β-Diketone Chelates, J. Phys. Chem.,1964, 68,3324; b) Relations between Intramolecular Energy Transfer Efficiences and Triplet State Energies in Rare Earth β-diketone Chelates, Chem. Soc. Japan, 1970, 43, 1955-1962.
61. F. W. J. Demnitz, B. A. Monteiro, M. N. Ramos and R. M. Srivastava, Heterocyclic
Communication, 1977, 3(2), 115.
62. H. D. Hartough, This Journal, 1948, 70, 1282.
63. Meisenheimer, Ber., 1926, 59, 1848.
64. a) P. Brougham, M. S. Cooper, D. A. Cummerson, H. Heaney and N. Thompson,
Synthesis, 1987, 1015-1017; b) A. R. Katritzky, Handbook of Heterocyclic Chemistry, Pergamon Press, Oxoford, 1 ed., 1985, 157.
65. C. Pederson, O. Buchardt, Acta Chem. Scand.,1970, 24, 2435; Fieser and Fieser’s
Reagents for Organic Synthesis, John Wiley & Sons, USA, 1989, 14. 66. E. Ochiai and Sai, J. Pharm. Soc. Japan, 1945, 65(B), 18.
67. a) D. M. Burness, Organic Syntheses, 1963, 4, 628; b) C. F. Allen and M. J. Kalm,
Organic Syntheses, 1963, 4, 616 c) W. M. D. Bryant and D. M. Smith, J.Amer. Chem. Soc.,1936, 58, 1014-1017.
68. A. R. Katritzky, E. W. Randal and L. E. Sutton, J. Chem. Soc., 1957, 1769.
69. D. V. Mayer, Chem. Abstr., 1965, 62, 10419c; A. M. Municio and A.Ribera, Chem.
Abstr., 1963, 59, 9971a.
70. I. C. L. Barros, C. C. C. Bejan, J. B. P. da Silva, F. W. J. Demnitz, H.-U. Gremlich,
J. Org. Chem., submetido em Maio de 2000.
71. J. March, Advanced Organic Chemistry, John Wiley and Sons, New York, 3 ed.,
72. a) I. D. Era, Can. J. Chem., 1968, 46, 2589-2595; b) M. J. Aroney, R. W. LeFèvre, ª
N. J. Singh, J. Chem. Soc.B, 1966, 1183; c) R. A. Russel, H. W. Thompson,
Spectrochim. Acta, 1956, 8, 138; d) C. J. Brown, D. E. C. Corbridge, Acta Cryst., 1954, 7, 711.
73. Pretsch, Clerk, Seilb, Simon, Tables of Spectral Data for Structure Determination of
Organic Compounds, Springer-Verlag, New York, 2 ed., 1989, I135-I190.
74. F. R. G. e Silva, Síntese, Caracterização e Análise dos Parâmetros de Intensidades
das Transições 4f-4f nos Complexos do Íon Európio Trivalente com Ligantes Derivados da Piridina, Tese de mestrado em Química, Departamento de Química
fundamental-UFPE, Recife, 1995.
75. C. C. C. da Silva, Uma Nova Classe de Compostos de Íons Lantanídeos
Luminescentes em Solução Aquosa: Síntese, caracterização e Estudos Espectroscópicos, Tese de mestrado em Química, Departamento de Química
fundamental-UFPE, Recife, 2000.
76. R. M. Silverstein, G. C. Bassler, T. C. Morril, Identificação Espectrométrica de
Compostos orgânicos, 3 ed., 1979, ch. 5.
77. N. Sabbatini, J.– M., Lehn, M. Guardigli, J. M. Coord. Chem. Rev., 1993, 123, 201.
78. D. A. Skoog, Principles of Instrumental Analysis, 2 ed, 1980, ch 23.
79. B.S. Santos, Supressão da Luminescência em Tropolonatos de Eu3+ e Tb3+: Uma
Investigação Espectroscópica – Dissertação de Mestrado em Química, Recife,
UFPE/Departamento de Química Fundamental, 1996, p.33-35.
80. S.A. Body, R. E. Kohrman and D.X. West, Inorg. Nucl. Chem. Lett., 1976, 12,
81. G. B. Rocha, SMLC II. Nova versão de Sparkles para o Cálculo de Complexos de
Lantanídeos: Conceito,Parâmetros para AM1, PM3 e MNDo e Teses – Dissertação de Mestrado, Departamento de Química Fundamental/UFPE; Recife, 1998.
82. G. F. de Sá, O.L. Malta, C. M. Donegá, A.M. Simas, R.L. Longo, P.A. Santa-Cruz,
E. F. da Silva Jr., Coordenation Chemistry Reviews, 2000, 196, 165-195.
83. G. A. Crosby, Molecular Crystals, 1966, 37-81.
84. C. K. Jorgensen and B. R. Judd, Mol. Phys., 1964, 8, 281.
85. S. A. Júnior, Estudos Espectroscópios de Complexos Mistos de β-dicetonas com
Íons Lantanídeos(III) – Tese de Doutorado em Química,
Recife:UFPE/Departamento de Química Fundamental, 1988.
86. H. Buzin, G. Mathis and S. Alves Jr., J. Luminescence, submetido 2000.
87. J.N. Demas, J. Chem. Educ., 1983, 60, 803.
88. C. M. Donegá, S. Alves. Jr. and G. F. de Sá, Chem. Commun., 1996, 1199-1200. 89. A. F. Kirby, D. Foster and F. S. Richardson, Chem. Phys. Letter, 1983, 95, 507.