Computational evaluation concerning the deviation of the atoms in 1- and 4-postions on the six-member ring and the effects on <sup>1</sup>HNMR chemical shift

doi:10.1007/s11458-011-0223-z

Front Chem Chin

0, Vol.

Issue () : 91-97 https://doi.org/10.1007/s11458-011-0223-z

RESEARCH ARTICLE

Computational evaluation concerning the deviation of the atoms in 1- and 4-postions on the six-member ring and the effects on ¹HNMR chemical shift

Asadollah FARHADI¹(

), Mohammad Ali TAKASSI¹, Hamid Reza MEMARIAN², Mousa SOLEYMANI

1. Faculty of Science, University of Petroleum Technology, Ahwaz 61981-44471, Iran; 2. Department of Chemistry, Faculty of Science, University of Isfahan, Isfahan 81746-73441, Iran

Download: PDF(250 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Abstract

Density functional theory (DFT) calculations were carried out on some cyclohexane derivatives to investigate the deviation atoms on the 1- and 4-positions of chair plane. The deviations of chair plane of two position in the cyclohexane derivatives were calculated at the B3LYP/6–31++ G(d, p) level. Furthermore, we investigated the correlation between deviations of two positions from chair plane on the chemical shift hydrogen atoms on the 4-position.

Keywords cyclohexane heterocyclohexane deviation B3LYP/6–31++G(d, p) chemical shift

Corresponding Author(s): FARHADI Asadollah,Email:farhadichem@yahoo.com

Issue Date: 05 June 2011

Cite this article:

Asadollah FARHADI,Mohammad Ali TAKASSI,Hamid Reza MEMARIAN, et al. Computational evaluation concerning the deviation of the atoms in 1- and 4-postions on the six-member ring and the effects on ¹HNMR chemical shift[J]. Front Chem Chin, 0, (): 91-97.

URL:

https://academic.hep.com.cn/fcc/EN/10.1007/s11458-011-0223-z
https://academic.hep.com.cn/fcc/EN/Y0/V/I/91

Fig.1 General structure of the cyclohexane and heterocyclohexane and those derivatives conformation and the numbering scheme used in this work.

Tab.1 Selected optimized geometrical parameter obtained for cylohexanes and heterocyclohexnes at B3LYP/6-31++ G(d,p) level of theory (bond lengths are given in ?). See Fig. 1 for numbering scheme.

Tab.2 The same as Table 1, but for heterocyclohexanes

Fig.2 General geometry defining deviations of the C, C and X atoms from the chair plane (C-C-C-C) in the cyclohexane, heterocyclohexane and their derivatives.

Fig.3 a) The trigonometric frame used for the calculation of the deviation of C atom (the height ) from the C-C-C-C plane, Fig. 2. b) A closer view of the triangle defining the height of C atom () from the C-C-C-C plane as described in part (a).

Tab.3 Calculation based on the geometries given in Fig. 2 and 3 by using relations (1)-(13) for the (C) and (C) (?) from chair plane (C-C-C-C) for cyclohexanes.

Tab.4 The same as Table 3, but for heterocyclohexanes.

Fig.4 Correlation between deviations of the C, C and X atoms from the chair ring plane and the type and position of the substituent on the ring for a) cyclohexanes and b) heterocyclohexanes

Tab.5 Chemical shift () of HNMR analysis of the axial and equatorial hydrogen (denoted with H and H respectively) atoms on the 1- and 4-positions that are calculated for cyclohexane and heterocyclohexane using Chem 3D. Ultra 8 method. See Fig. 1 for sign scheme.

Tab.6 The same as Table 5, but for heterocyclohexanes.

Tab.7 Observed proton chemical shifts of some of cyclohexanes and analogs [,]

1	Walker, J. D.; Colwell, R. R., Appl. Environ. Microbiol. 1976, 31, 189-197 pmid:999271
2	Solano-Serena, F.; Marchal, R.; Lebeault, J. M.; Vandecasteele, J. P., Lett. Appl. Microbiol. 2000, 30, 19-22 doi: 10.1046/j.1472-765x.2000.00631.x pmid:10728554
3	Brzostowicz, P. C.; Walters, D. M.; Jackson, R. E.; Halsey, K. H.; Ni, H.; Rouvière, P. E., Environ. Microbiol. 2005, 7, 179-190 doi: 10.1111/j.1462-2920.2004.00681.x pmid:15658985
4	Mannsville, C. P. S., Cyclohexane; Mannsville Chemical Products Corporation, New York, 1993
5	Uribe, S.; Rangel, P.; Espínola, G.; Aguirre, G., Appl. Environ. Microbiol. 1990, 56, 2114-2119 pmid:2202257
6	.Available from<http://chemicalland21.com/>in 2006/07/20.
7	Sachse, H., Berichte 1890, 23, 1363-1370
8	Tomé, L. I. N.; Rosado, M. T. S.; Eusébio, M. E. S.; Redinha, J. S., J. Mol. Struct. THEOCHEM 2007, 804, 65-67
9	Kleinpeter, E.; B?lke, U.; Frank, A., Tetrahedron 2008, 64, 10014-10017 doi: 10.1016/j.tet.2008.07.024
10	Kassaee, M. Z.; Arshadi, S.; Beigi, M., J. Mol. Struct. THEOCHEM 2002, 589-590, 153-159 doi: 10.1016/S0166-1280(02)00257-9
11	Ko?nik, W.; Bocian, W.; Chmielewski, M.; Tvaro?ka, I., Carbohydr. Res. 2008, 343, 1463-1472 doi: 10.1016/j.carres.2008.03.032 pmid:18456248
12	Dega-Szafran, Z.; Dutkiewicz, G.; Fojud, Z.; Kosturkiewicz, Z.; Szafran, M., J. Mol. Struct. THEOCHEM 1971, 9, 447-454
13	Geise, H. J.; Buys, H. R.; Mijlhoff, F. C., J. Mol. Struct. THEOCHEM 1981, 46, 1959-1962
14	Allinger, N. L.; Hirsch, J. A.; Miller, M. A.; Tyminski, I. J.; VanCatledge, F. A., J. Am. Chem. Soc. 1968, 90, 1199-1210 doi: 10.1021/ja01007a017
15	Van de Graaf, B.; Baas, J. M. A.; Wepster, B. M., Recl. Trav. Chim. Pays Bas 1978, 97, 268-273 doi: 10.1002/recl.19780971008
16	Baas, J. M. A.; Van de Graaf, B.; Van Veen, A.; Wepster, B. M., Recl. Trav. Chim. Pays Bas 1980, 99, 228-233 doi: 10.1002/recl.19800990703
17	Antúnez, S.; Juaristi, E., J. Org. Chem. 1996, 61, 6465-6469 doi: 10.1021/jo960337c pmid:11667498
18	Allinger, N. L.; Miller, M. A., J. Am. Chem. Soc. 1961, 83, 2145-2148 doi: 10.1021/ja01470a024
19	Kellie, G. M.; Riddell, F. G., Top. Stereochem. 1974, 8, 225-269 doi: 10.1002/9780470147177.ch3
20	Squillacote, M. R.; Sheridan, S.; Chapman, O. L.; Anet, F. A. L., J. Am. Chem. Soc. 1975, 97, 3244-3246 doi: 10.1021/ja00844a068
21	Jensen, F. R.; Bushweller, C. H.; Beck, B. H., J. Am. Chem. Soc. 1969, 91, 344-351 doi: 10.1021/ja01030a023
22	Li, G.; Xu, M.; Larsen, S. C.; Grassian, V. H., J. Mol. Catal. Chem. 2003, 194, 169-180 doi: 10.1016/S1381-1169(02)00518-6
23	Hao, J.; Wang, J.; Wang, Q.; Yu, Y.; Cai, S.; Zhao, F., Appl. Catal. A Gen. 2009, 368, 29-34 doi: 10.1016/j.apcata.2009.08.007
24	Anisia, K. S.; Kumar, A., J. Mol. Catal. Chem. 2007, 271, 164-179 doi: 10.1016/j.molcata.2007.02.045
25	Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A. Jr; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ciolowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A., Gaussian 98; Gaussian Inc., Pittsburg PA , 1998
26	Silverstein, R. M.; Clayton Bassler, G.; Morrill, T., Spectrometric Identification of Organic Compound; 5th Edition, New York , 1991
27	Pretsch, E.; Clerc, T.; Seibl, J.; Simon, W., Tabellen zur Structuraufkl?rang organischerVerbindurgen, springer-verlag, Berlin Heidelberg, New York, 1989
28	Abraham, R. J.; Warne, M. A.; Griffiths, L., J. Chem. Soc. Perki Trans. 2 1997, 2, 31-39 doi: 10.1039/a604567g

Viewed

Full text

Abstract

Cited

Shared

Discussed