Abstract
α-Parabutylchloral (2,4,6-tris(1′,1′,2′-trichloropropyl)-1,3,5-trioxane, C12H15Cl9O3) crystallizes in the orthorhombic space groupP212121 (No. 19) witha=12.165(6),b=9.964(5),c=17.433(9) Å,Z=4. The finalR value is 0.043 for 1667 observed reflections.β-Parabutylchloral crystallizes in the orthorhombic space groupPna21 (No. 33), witha=12.387(6),b=10.488(5),c=16.605(8) Å,Z=4. The finalR value is 0.047 for 1417 observed reflections.
Unlike the geometric isomersα- andβ-parachloral (CCl3CHO)3 which exist in boat andcis,cis-chair conformations, theα- andβ-forms of parabutylchloral (CH3CHClCCl2CHO)3 are now shown by X-ray crystallography not to be geometric isomers. Both forms exist incis,cis-chair conformations and the isomerism arises from the chirality of the side chains at theβ-carbon atoms. In theα-form only two of the side chains have the same chirality, but in theβ-form the chirality at all theβ-carbon atoms is the same. The X-ray results are supplemented by1H and13C nuclear magnetic resonance spectroscopy and by mass spectrometry.
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References
Baron, M. (1967)Recl. Trav. Chim. 86, 561.
Baron, M., and Hollis, D. P. (1964)Recl. Trav. Chim. 83, 391.
Baron, M., Brieux de Mandirola, O., and Westerkamp, J. F. (1963)Can. J. Chem. 41, 1893.
Béhal, A., and Choay, E. (1892)Ann. Chim. Phys. 26, 7.
Burstyn, W. (1902)Sitzungsber. Wiener Akad., 511.
Bussetti, V., Mammi, M., and Carazzolo, G. (1963)Z. Kristallogr. 119, 310.
Bussetti, V., Del Pra, A., and Mammi, M. (1969)Acta Cryst. B 25, 1191.
Carpenter, D. C., and Brockway, L. O. (1936)J. Am. Chem. Soc. 58, 1270.
Chattaway, F. D., and Kellett, E. G. (1928)J. Chem. Soc., 2709.
Craven, E. C., Jowitt, H., and Ward, W. R. (1962)J. Appl. Chem. 12, 526.
Diana, G., and Ganis, P. (1963)Atti Accad. Naz. Lincei 35, 80.
Hay, D. G., and Mackay, M. F. (1980)Acta Cryst. B 36, 2367.
Helferich, B., and Besler, E. (1924),Chem. Ber. 57, 1276.
Irving, A., Archer, S. J., and Nassimbeni, L. R. (1982) unpublished results.
Jungnickel, J. L., and Reilly, C. A. (1965)Recl. Trav. Chim. 84, 1526.
Lemieux, R. U., Kullnig, R. K., Bernstein, H. F., and Schneider, W. G. (1958)J. Am. Chem. Soc. 80, 6098.
McCallum, P. A., Irving, H. M. N. H., and Nassimbeni, L. R. (1980)Acta Cryst. B 36, 1626.
Novak, A., and Whalley, E. (1958)Can. J. Chem. 36, 1116.
Ropp, G. A., Craig, W. E., and Raden, V. (1963)Organic Syntheses, Vol. IV (Wiley, New York), p. 131.
Sheldrick, G. M. (1978)Computing in Crystallography (Delft University Press).
Sheldrick, G. M. (1984) private communication.
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We thank the CSIR (Pretoria) for collecting the diffractometer data, the CSIR and the University of Cape Town for research grants, Dr. M. L. Niven for crystallographic assistance, and Miss C. Angus for preparing parabutylchloral and separating the isomers. The 500 MHz NMR data are courtesy of Mr. Ivan Antonowitz of the CSIR.
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Archer, S.J., Irving, H.M.N.H., Koch, K.R. et al. Isomerism in parabutylchloral; x-ray crystallographic determinations of 2,4,6-tris(1′,1′,2′-trichloropropyl)-1,3,5-trioxanes. Journal of Crystallographic and Spectroscopic Research 15, 333–349 (1985). https://doi.org/10.1007/BF01160726
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DOI: https://doi.org/10.1007/BF01160726