Synthesis and Conformational Assignment of N-(E)-Stilbenyloxymethylenecarbonyl-Substituted Hydrazones of Acetone and o -( m - and p -) Chloro- (nitro-) benzaldehydes by Means of and NMR Spectroscopy
Eighteen new N-(E)-stilbenyloxyalkylcarbonyl-substituted hydrazones of ortho- (meta- and para-) chloro- (nitro-) benzaldehydes 1–18 and two analogous hydrazones of acetone 19-20 were prepared. The stereochemical behavior of 1–18 in dimethyl-d6 sulfoxide solution has been studied by NMR and NMR techniques, using spectral data of 19 and 20 as supporting material. The E-geometrical isomers and cis-/trans-amide conformers have been found for these hydrazones. Energy barriers of isomers are reported. 1. Introduction The N-substituted hydrazones of aldehydes are of interest because of their biological and pharmacological activities [1–5], as well as considerable chelating power with transition metals [6–9]. They can be used in analytical chemistry to cover and analyze metals selectively as hydrazone complexes. Hydrazones of o-(m- and p-) chlorobenzaldehydes and o-(m- and p-) nitrobenzaldehydes have been reported in the literature [10–13]. Chloro- and nitrobenzaldehydes are widely used as reagents for organic synthesis, chiefly as reactants for manufacturing pharmaceuticals, plastic additives, pesticides, dyes and metal finishing agents. For example, 2-chlorobenzaldehyde is an intermediate for the optical brighteners production and finds its application as the brightening agent for zinc plating, whereas 2-nitrobenzaldehyde is a substrate for indigo synthesis in the Baeyer-Drewson method [14] and easy removable protection group for many functionalities [15]. However, despite the many synthetic applications of substituted benzaldehydes, to the best of our knowledge no work has been published in the literature about the synthesis and physicochemical properties of N-(E)-stilbenyloxyalkylcarbonyl substituted hydrazones of ortho- (meta- and para-) chloro- and (nitro-) benzaldehydes. These compounds, containing amide and hydrazone functions in their molecules, seemed to be suitable candidates for further chemical modifications and may be pharmacologically active and analytically useful. It ought to be pointed out that (E)-stilbenes hydroxylated at one to five positions as well as their ethereal derivatives are produced by woody plants and exhibit a broad spectrum of biological activity [16–20]. We have previously reported the synthesis, physicochemical properties, as well as mass spectrometric study of N-(E)-stilbenyloxyalkylcarbonyl substituted hydrazones of o-(m- and p-) hydroxybenzaldehydes and 2-(3- and 4-)pyridinecarboxyaldehydes [21–26]. Our studies have been recently extended to N-(E)-stilbenyloxymethylenecarbonyl substituted hydrazones of o-(m- and p-)
References
[1]
P. Vicini, F. Zani, P. Cozzini, and I. Doytchinova, “Hydrazones of 1,2-benzisothiazole hydrazides: synthesis, antimicrobial activity and QSAR investigations,” European Journal of Medicinal Chemistry, vol. 37, no. 7, pp. 553–564, 2002.
[2]
G. Turan-Zitouni, Y. Blache, and K. Güven, “Synthesis and antimicrobial activity of some imidazo-[1,2-a]pyridine-2-carboxylic acid arylidenehydrazide derivatives,” Bollettino Chimico Farmaceutico, vol. 140, no. 6, pp. 397–400, 2001.
[3]
S. Takaji, H. Hibasami, I. Imoto et al., “Growth inhibition of Helicobacter pylori by a polyamine synthesis inhibitor, methylglyoxal bis(cyclopentylamidinohydrazone),” Letters in Applied Microbiology, vol. 25, no. 3, pp. 177–180, 1997.
[4]
B. N. Dobrova, A. S. Dimoglo, and Y. M. Chumakov, “Study of the relationship between chemical structure and antimicrobial activity in a series of hydrazine-based coordination compounds,” Drug Research, vol. 50, no. 8, pp. 747–751, 2000.
[5]
V. M. Naik and N. B. Mallur, “Synthesis and characterization of niobium(V) complexes with terdentate ONO donor hydrazones,” Indian Journal of Chemistry A, vol. 41, no. 4, pp. 780–784, 2002.
[6]
P. Domiano, C. Pelizzi, G. Predieri, C. Vignalli, and G. Palla, “Aroylhydrazones as chelating agents: d10-metal complexes of pyridine-2-carbaldehyde salicyloylhydrazone and x-ray structure of the zinc derivative,” Polyhedron, vol. 3, no. 3, pp. 281–286, 1984.
[7]
M. Gallego, M. Garcia-Vargas, and M. Valcarcel, “Pyridine-2-carbaldehyde 2-hydroxybenzoylhydrazone as a selective reagent for the extraction and spectrophotometric determination of iron(II),” The Analyst, vol. 104, no. 1239, pp. 613–619, 1979.
[8]
A. Casoli, A. Mangia, and G. Predieri, “Determination of uranium by reversed-phase high-performance liquid chromatography,” Analytical Chemistry, vol. 57, no. 2, pp. 561–563, 1985.
[9]
P. R. Mandlik, S. R. Aswale, and A. S. Aswar, “Chromium(III), manganese(III), iron(III), oxovanadium(II), zirconium(IV) and dioxouranium(II) complexes of hydrazone of isonicotinic acid hydrazide,” Journal of the Indian Chemical Society, vol. 79, no. 8, pp. 689–692, 2002.
[10]
C. Glidewell, J. N. Low, J. M. S. Skakle, and J. L. Wardell, “Hydrogen-bonded dimers in 2-nitrobenzaldehyde hydrazone and a three-dimensional hydrogen-bonded framework in 3-nitrobenzaldehyde hydrazone,” Acta Crystallographica Section C, vol. 60, no. 9, pp. o686–o689, 2004.
[11]
C. Glidewell, J. N. Low, J. M. S. Skakle, and J. L. Wardell, “Hydrogen bonding in nitroaniline analogues: 4-nitrobenzaldehyde hydrazone forms hydrogen-bonded sheets of R44(26) rings,” Acta Crystallographica C, vol. 60, no. 1, pp. o33–o34, 2004.
[12]
A. V. Shastin, V. N. Korotchenko, V. G. Nenajdenko, and E. S. Balenkova, “A novel synthetic approach to dichlorostyrenes,” Tetrahedron, vol. 56, no. 35, pp. 6557–6563, 2000.
[13]
V. Z. Shirinian, L. I. Belen'kii, and M. M. Krayushkin, “A convenient method for the preparation of N-unsubstituted hydrazones of aromatic ketones and aldehydes,” Russian Chemical Bulletin, vol. 48, no. 11, pp. 2171–2172, 1999.
[14]
H. Schmidt, “Indigo—100 jahre industrielle synthese,” Chemie in Unserer Zeit, vol. 31, no. 3, pp. 121–128, 1997.
[15]
P. ？ebej, T. ？olomek, L. Hroudná, P. Brancová, and P. Klán, “Photochemistry of 2-nitrobenzylidene acetals,” Journal of Organic Chemistry, vol. 74, no. 22, pp. 8647–8658, 2009.
[16]
G. Bielek and H. Kindl, ？sterreichische Chemiker-Zeitung, vol. 63, pp. 273–281, 1962.
[17]
T. P. Schultz, T. F. Hubbard, L. Jin, T. H. Fisher, and D. D. Nicholas, “Role of stilbenes in the natural durability of wood: fungicidal structure-activity relationships,” Phytochemistry, vol. 29, no. 5, pp. 1501–1507, 1990.
[18]
T. P. Schultz, W. D. Boldin, T. H. Fisher, D. D. Nicholas, K. D. Mcmurtrey, and K. Pobanz, “Structure-fungicidal properties of some 3- and 4-hydroxylated stilbenes and bibenzyl analogues,” Phytochemistry, vol. 31, no. 11, pp. 3801–3806, 1992.
[19]
S. Renaud and M. De Lorgeril, “Wine, alcohol, platelets, and the French paradox for coronary heart disease,” The Lancet, vol. 339, no. 8808, pp. 1523–1526, 1992.
[20]
J.-R. Dai, Y. F. Hallock, J. H. Cardellina II, and M. R. Boyd, “HIV-inhibitory and cytotoxic oligostilbenes from the leaves of Hopea malibato,” Journal of Natural Products, vol. 61, no. 3, pp. 351–353, 1998.
[21]
E. Wyrzykiewicz and D. Pruka？a, “New isomeric N-substituted hydrazones of 2-, 3-and 4-pyridinecarboxaldehydes,” Journal of Heterocyclic Chemistry, vol. 35, no. 2, pp. 381–387, 1998.
[22]
E. Wyrzykiewicz and A. Blaszczyk, “New isomeric N-substituted hydrazones of 2-, 3- and 4-pyridinecarboxaldehydes and methyl-3-pyridylketone,” Journal of Heterocyclic Chemistry, vol. 37, no. 4, pp. 975–981, 2000.
[23]
E. Wyrzykiewicz, A. Blaszczyk, and I. Turowska-Tyrk, “N-(E)-2-stilbenyloxymethylenecarbonyl substituted hydrazones of ortho, meta and para hydroxybenzaldehydes,” Bulletin of the Polish Academy of Sciences, vol. 48, no. 3, pp. 213–229, 2000.
[24]
E. Wyrzykiewicz and D. Pruka？a, “New isomeric N-substituted hydrazones of ortho, meta and para hydroxybenzaldehydes,” Polish Journal of Chemistry, vol. 72, no. 4, pp. 694–702, 1998.
[25]
E. Wyrzykiewicz and D. Pruka？a, “EIMS study of new isomeric N-substituted hydrazones of 2-(3- and 4-)- pyridinecarboxaldehydes,” Journal of Heterocyclic Chemistry, vol. 36, no. 3, pp. 739–745, 1999.
[26]
E. Wyrzykiewicz and D. Prukala, “Electron impact-induced mass spectral study of new isomeric N-substituted hydrazones of ortho-, meta- and para-hydroxybenzaldehydes,” European Journal of Mass Spectrometry, vol. 5, no. 3, pp. 183–190, 1999.
[27]
G. Palla, G. Predieri, P. Domiano, C. Vignali, and W. Turner, “Conformational behaviour and E/Z isomerization of N-acyl and N-aroylhydrazones,” Tetrahedron, vol. 42, no. 13, pp. 3649–3654, 1986.
[28]
E. A. Braude, “Studies in light absorption. Part VIII. Dibenzyl and stilbene derivatives. Interaction between unconjugated chromophores,” Journal of the Chemical Society, pp. 1902–1909, 1949.
[29]
M. Calvin and H. Ward Alter, “Substituted stilbenes. I. absorption spectra,” The Journal of Chemical Physics, vol. 19, no. 6, pp. 765–767, 1951.
[30]
D. F. Detar and L. A. Carpino, “The preparation of and the spectral characteristics of some 2-substituted cis- and trans-stilbenes,” Journal of the American Chemical Society, vol. 78, no. 2, pp. 475–479, 1956.
[31]
M. Oki and H. Kunimoto, “The characteristic infrared absorption bands of cis-stilbene and its p,p'-disubstituted derivatives,” Spectrochimica Acta, vol. 19, no. 9, pp. 1463–1471, 1963.
[32]
H. Shanan-Atidi and K. H. Bar-Eli, “A convenient method for obtaining free energies of activation by the coalescence temperature of an unequal doublet,” Journal of Physical Chemistry, vol. 74, no. 4, pp. 961–963, 1970.
[33]
G. Palla, C. Pelizzi, G. Predieri, and C. Vignali, Gazzetta Chimica Italiana, vol. 112, p. 339, 1982.
[34]
E. Wyrzykiewicz, J. K？pka, and W. Pruka？a, Polish Journal of Chemistry, vol. 62, pp. 251–255, 1988.
[35]
E. Wyrzykiewicz, Annales Societatis Chimicae Polonorum, vol. 42, pp. 347–351, 1968.
