Facile Preparation of 1,2-Diols from Chalcones: An NMR Spectroscopy and X-Ray Crystallography Study
Author(s)
Marco A. Obregón-Mendoza1,
María Miriam Estévez-Carmona1,
Carolina Escobedo-Martínez2,
Manuel Soriano-García1*,
Raúl G. Enríquez1*
Affiliation(s)
1 Instituto de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, México City, México. 2 Departamento de Farmacia, División de Ciencias Naturales y Exactas del Campus Guanajuato, Universidad de Guanajuato, México.
1 Instituto de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, México City, México. 2 Departamento de Farmacia, División de Ciencias Naturales y Exactas del Campus Guanajuato, Universidad de Guanajuato, México.
ABSTRACT
Structures of 2-(naphthalen-2-ylmethyl)-2,3-dihydro-1H-indene-1,2-diol (C20H18O2), compound 1 and 1-(3,4-dimethoxyphenyl)-3-methoxy-3-(4-nitrophenyl)propane-1,2-diol chloroform (C18H21NO7·CHCl3) compound 2 were established by spectral and X-ray diffraction studies. Compound 1 crystallizes in the orthorhombic space group P212121 with unit cell parameters a = 5.2177 (6), b = 13.903 (2), c = 21.121 (2) A, Z = 4. Compound 2 crystallizes in the triclinic space group P-1 with unit cell parameters a = 9.238 (1), b = 9.879 (1), c = 12.636 (1) A, α = 102.004 (1), β = 92.356 (1), γ = 90.779 (1)o, Z = 2. These two new molecules arise from a facile preparation of 1,2-diols from chalcones and have been fully characterized. Based on the crystallographic information obtained for compound 1, the relative configuration for the chiral centers is 1S and 2S. In structure 1, both hydroxyl groups adopt an anti-conformation with a torsion angle O1-C1-C2-O2 value of 93.1 (2)o [in molecule 2, both hydroxyl groups adopt a trans-conformation with a torsion angle O1-C1-C2-O2 value of －171.0 (2)。]. In both structures, the molecules in the crystal are linked by intermolecular hydrogen bonds O-H···O and C-H···O interactions and adjacent molecules are interconnected by intermolecular weak C-H···π and C-H···Cl interactions which give additional support to molecular packing stability.
Structures of 2-(naphthalen-2-ylmethyl)-2,3-dihydro-1H-indene-1,2-diol (C20H18O2), compound 1 and 1-(3,4-dimethoxyphenyl)-3-methoxy-3-(4-nitrophenyl)propane-1,2-diol chloroform (C18H21NO7·CHCl3) compound 2 were established by spectral and X-ray diffraction studies. Compound 1 crystallizes in the orthorhombic space group P212121 with unit cell parameters a = 5.2177 (6), b = 13.903 (2), c = 21.121 (2) A, Z = 4. Compound 2 crystallizes in the triclinic space group P-1 with unit cell parameters a = 9.238 (1), b = 9.879 (1), c = 12.636 (1) A, α = 102.004 (1), β = 92.356 (1), γ = 90.779 (1)o, Z = 2. These two new molecules arise from a facile preparation of 1,2-diols from chalcones and have been fully characterized. Based on the crystallographic information obtained for compound 1, the relative configuration for the chiral centers is 1S and 2S. In structure 1, both hydroxyl groups adopt an anti-conformation with a torsion angle O1-C1-C2-O2 value of 93.1 (2)o [in molecule 2, both hydroxyl groups adopt a trans-conformation with a torsion angle O1-C1-C2-O2 value of －171.0 (2)。]. In both structures, the molecules in the crystal are linked by intermolecular hydrogen bonds O-H···O and C-H···O interactions and adjacent molecules are interconnected by intermolecular weak C-H···π and C-H···Cl interactions which give additional support to molecular packing stability.
Cite this paper
Obregón-Mendoza, M. , Estévez-Carmona, M. , Escobedo-Martínez, C. , Soriano-García, M. and Enríquez, R. (2015) Facile Preparation of 1,2-Diols from Chalcones: An NMR Spectroscopy and X-Ray Crystallography Study. International Journal of Organic Chemistry, 5, 137-146. doi: 10.4236/ijoc.2015.53015.
Obregón-Mendoza, M. , Estévez-Carmona, M. , Escobedo-Martínez, C. , Soriano-García, M. and Enríquez, R. (2015) Facile Preparation of 1,2-Diols from Chalcones: An NMR Spectroscopy and X-Ray Crystallography Study. International Journal of Organic Chemistry, 5, 137-146. doi: 10.4236/ijoc.2015.53015.
References
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http://dx.doi.org/10.1021/ja001460v [3] Periasamy, M. and Thirumalaikumar, M. (2000) Methods of Enhancement of Reactivity and Selectivity of Sodium Borohydride for Applications in Organic Synthesis. Journal of Organometallic Chemistry, 609, 137-151.
http://dx.doi.org/10.1016/S0022-328X(00)00210-2 [4] Fuji, H., Ohima, K. and Utimoto, K. (1991) A Facile and Selective 1,2-Reduction of Conjugated Ketones with NaBH4 in the Presence of CaCl2. Chemistry Letters, 20, 1847-1848.
http://dx.doi.org/10.1246/cl.1991.1847 [5] Baluja, M.G., Municio, A.M. and Vega, S. (1964) Reactivity of lO,p-Unsaturated Ketones toward Sulfhydryl Compounds and Their Antifungal Activity. Chemistry and Industry (London), 50, 2053. [6] Dimmock, J.R., Raghavan, S.K., Logan, B.M. and Bigam, G.E. (1983) Antileukemic Evaluation of Some Mannich Bases Derived from 2-Arylidene-1,3-diketones. European Journal of Medicinal Chemistry, 18, 248-254. [7] Armarego, W.L.F. and Perrin, D.D. (1997) Purification of Laboratory Chemicals. 4th Edition, Butterworth-Heinemann, Oxford. [8] Bruker (2009) APEX2, SAINT and SADABS. Bruker AXS Inc., Madison. [9] Sheldrick, G.M. (2007) A Short History of SHELX. Acta Crystallographica, A64, 112-122.
http://dx.doi.org/10.1107/S0108767307043930 [10] Flack, H.D. (1983) Onenantiomorph-Polarity Estimation. Acta Crystallographica, A39, 876-881.
http://dx.doi.org/10.1107/S0108767383001762 [11] Brandenburg, K. (2006) DIAMOND. Version 3.1c. Crystal Impact GbR, Bonn. [12] Farrugia, L.J. (2012) WinGX and ORTEP for Windows: An Update. Journal of Applied Crystallography, 45, 849-854.
http://dx.doi.org/10.1107/S0021889812029111 [13] Nardelli, M. (1983) PARST: A System of Fortran Routines for Calculating Molecular Structure Parameters from Results of Crystal Structure Analyses. Computers & Chemistry, 7, 95-98.
http://dx.doi.org/10.1016/0097-8485(83)85001-3 [14] Nardelli, M. (1995) PARST95—An Update to PARST: A System of Fortran Routines for Calculating Molecular Structure Parameters from the Results of Crystal Structure Analyses. Journal of Applied Crystallography, 28, 659.
http://dx.doi.org/10.1107/S0021889895007138 [15] Bernstein, J., Davis, R.E., Shimoni, L. and Chamg, N.-L. (1995) Patterns in Hydrogen Bonding: Functionality and Graph Set Analysis in Crystals. Angewandte Chemie International Edition (English), 34, 1555-1573.
http://dx.doi.org/10.1002/anie.199515551
[1] Corey, E.J. and Winter, R.A.E. (1963) A New, Stereospecific Olefin Synthesis from 1,2-Diols. Journal of the American Chemical Society, 85, 2677-2678.
http://dx.doi.org/10.1021/ja00900a043 [2] Notz, W. and List, B. (2000) Catalytic Asymmetric Synthesis of Anti-1,2-diols. Journal of the American Chemical Society, 122, 7386-7387.
http://dx.doi.org/10.1021/ja001460v [3] Periasamy, M. and Thirumalaikumar, M. (2000) Methods of Enhancement of Reactivity and Selectivity of Sodium Borohydride for Applications in Organic Synthesis. Journal of Organometallic Chemistry, 609, 137-151.
http://dx.doi.org/10.1016/S0022-328X(00)00210-2 [4] Fuji, H., Ohima, K. and Utimoto, K. (1991) A Facile and Selective 1,2-Reduction of Conjugated Ketones with NaBH4 in the Presence of CaCl2. Chemistry Letters, 20, 1847-1848.
http://dx.doi.org/10.1246/cl.1991.1847 [5] Baluja, M.G., Municio, A.M. and Vega, S. (1964) Reactivity of lO,p-Unsaturated Ketones toward Sulfhydryl Compounds and Their Antifungal Activity. Chemistry and Industry (London), 50, 2053. [6] Dimmock, J.R., Raghavan, S.K., Logan, B.M. and Bigam, G.E. (1983) Antileukemic Evaluation of Some Mannich Bases Derived from 2-Arylidene-1,3-diketones. European Journal of Medicinal Chemistry, 18, 248-254. [7] Armarego, W.L.F. and Perrin, D.D. (1997) Purification of Laboratory Chemicals. 4th Edition, Butterworth-Heinemann, Oxford. [8] Bruker (2009) APEX2, SAINT and SADABS. Bruker AXS Inc., Madison. [9] Sheldrick, G.M. (2007) A Short History of SHELX. Acta Crystallographica, A64, 112-122.
http://dx.doi.org/10.1107/S0108767307043930 [10] Flack, H.D. (1983) Onenantiomorph-Polarity Estimation. Acta Crystallographica, A39, 876-881.
http://dx.doi.org/10.1107/S0108767383001762 [11] Brandenburg, K. (2006) DIAMOND. Version 3.1c. Crystal Impact GbR, Bonn. [12] Farrugia, L.J. (2012) WinGX and ORTEP for Windows: An Update. Journal of Applied Crystallography, 45, 849-854.
http://dx.doi.org/10.1107/S0021889812029111 [13] Nardelli, M. (1983) PARST: A System of Fortran Routines for Calculating Molecular Structure Parameters from Results of Crystal Structure Analyses. Computers & Chemistry, 7, 95-98.
http://dx.doi.org/10.1016/0097-8485(83)85001-3 [14] Nardelli, M. (1995) PARST95—An Update to PARST: A System of Fortran Routines for Calculating Molecular Structure Parameters from the Results of Crystal Structure Analyses. Journal of Applied Crystallography, 28, 659.
http://dx.doi.org/10.1107/S0021889895007138 [15] Bernstein, J., Davis, R.E., Shimoni, L. and Chamg, N.-L. (1995) Patterns in Hydrogen Bonding: Functionality and Graph Set Analysis in Crystals. Angewandte Chemie International Edition (English), 34, 1555-1573.
http://dx.doi.org/10.1002/anie.199515551