Structural and conformational features of "heterogeneous" naphthophosphacyclophanes on the basis of 1,6-dihydroxynaphthalene

Authors: Slitikov P.V. Published: 15.06.2016
Published in issue: #3(66)/2016  
DOI: 10.18698/1812-3368-2016-3-110-117

Category: Chemistry | Chapter: Organic Chemistry  
Keywords: dihydroxynaphthalenes, naphthophosphacyclophanes, NMR spectroscopy, semiempirical methods, quantum-chemical methods

The aim of this research was to carry out computer modeling of "heterogeneous" naphthophosphacyclophanes synthesized by molecular integration. One of the structural units is represented by asymmetric 1,6-dihydroxynaphthalene, and the other one is based on dihydroxynaphtalene with the most remoted in space hydroxogroups (1,7-, 2,6-and 2,7-dihydroxynaphthalenes). Amides of phosphite with different substituents at the phosphorus atom perform as an aliphatic linker in macrocyclic systems. Moreover, we calculated the equilibrium geometry of the molecules of synthesized "heterogeneous" naphthophosphacyclophanes and we applied RM1 semiemperical method and quantum-chemical calculations ab initio HF (3-21G). Based on comparative analysis of 1H and 31P NMR spectroscopy data as well as semi-empirical method RM1 data, we determined the optimal configuration of the synthesized naphthocyclophanes. The findings of the research show that the mutual arrangement of aromatic fragments depends on structural features of initial dihydroxynaphthalenes.


[1] Steed W.J., Atwood J.L. Supramolecular chemistry. John Wiley & Sons, Ltd, 2000. 772 p.

[2] Nifantyev E.E., Slitikov P.V., Rasadkina E.N. Synthesis of arylenephosphamacrocycles using tri- and pentavalent phosphorus compounds. Russ. Chem. Rev., 2007, 76 (4), pp. 327-338. DOI: 10.1070/RC2007v076n04ABEH003667

[3] Knyazeva I.R., Burilov A.R., Pudovik M.A., Khabikher V.D. Phosphorus-containing macrocyclic compounds: synthesis and properties. Russ. Chem. Rev., 2013, 82 (2), pp. 150-186. DOI: 10.1070/RC2013v082n02ABEH004296

[4] Slitikov P.V., Evdokimenkova Yu.B., Rasadkina E.N., Vasyanina L.K., Nifantiev E.E. Synthesis and Characterization of Phosphamacrocycles on the Basis of 2,7-Dihydroxynaphthalene. Macroheterocycles, 2011, vol. 4, no. 4, pp. 311323 (in Russ.). DOI: 10.6060/mhc2011.4.07

[5] Slitikov P.V., Rasadkina E.N., Vasyanina L.K., Nifantiev E.E. 2,6-Dihydroxynaphthalene in the Synthesis of Naphthophosphacyclophanes. Macroheterocycles, 2013, vol. 6, no. 2, pp. 170-179 (in Russ.). DOI: 10.6060/mhc130117s

[6] Slitikov P.V., Rasadkina E.N., Vasyanina L.K., Nifantiev E.E. The Cyclic Bisamidophosphites on the Basis of 1,6-dihydroxynaphthalene. Izv. AN. Ser. Khim. [Russ. Chem. Bull., 2014, 63 (9), 2023-2031], 2014, no. 9, pp. 2023-2031 (in Russ.). DOI: 10.1007/s11172-013-0293-9

[7] Rasadkina E.N., Slitikov P.V., Mel’nik M.S., Nifantiev E.E. Synthesis and study of "nonuniform" naphthylenephosphacyclophanes. Izv. AN. Ser. Khim. [Russ. Chem. Bull., 2004, 53 (2), 372-382], 2004, no. 2, pp. 362-368 (in Russ.). DOI: 10.1023/B:RUCB.0000030814.65039.1a

[8] Slitikov P.V. Preparation and properties of inhomogeneous naphthophosphacyclophans on the 1,6-dihydroxynaphthalene-base. Jelektr. nauchno-tekh. izd. "Inzhenernyy zhurnal: nauka i innovacii" [El. Sci.-Tech. Publ. "Eng. J.: Science and Innovation"], 2012, iss. 11. DOI: 10.18698/2308-6033-2012-11-434 Available at: http://engjournal.ru/eng/catalog/fundamentals/chem/434.html

[9] Slitikov P.V. Structural features of naphthaphosphacyclofanes based on dihydroxynaphthlenes. Vestn. Mosk. Gos. Tekh. Univ. im. N.E. Baumana, Estestv. Nauki [Herald of the Bauman Moscow Tech. Univ., Nat. Sci.], 2014, no. 1, pp. 94-105 (in Russ.).

[10] Nifantiev E.E., Rasadkina E.N., Evdokimenkova Yu.B. Synthesis of cavity systems by cyclophosphorylation of 1,7-dihydroxynaphthalene with phosphorous triamides. Russ. Chem. Bull., 2001, 50 (5), pp. 923-924. DOI: 10.1023/A:1011392017095.

[11] Nifantiev E.E., Rasadkina E.N., Evdokimova Yu.B., Stash A.I., Belsky V.K., Vasyanina L.K. Cyclo[bis(1,7-naphthylenedialkylamidophosphites)]. Heteroatom Chem, 2003, vol. 14, no. 5, pp. 404-412. DOI: 10.1002/hc.10143

[12] Rocha G.B., Freire R.O., Simas A.M., Stewart J.J.P. RM1: A reparameterization of AM1 for H, C, N, O, P, S, F, Cl, Br and I. J. Comp. Chem, 2006, vol. 27, no. 10, pp. 1101-1111. DOI: 10.1002/jcc.20425

[13] Holtje H.-D., Sippl W., Rognan D., Folkers G. Molecular Modeling. Basic principles and application. WILEY-VCH Verlag GmbH & Co. KGaA, 2008. 315 p.

[14] Rasadkina E.N., Nifantiev E.E. Dioxaphosphacyclophanes - new type of doubledeck systems. Zhurnal Obshchey Khimii [Russ. J. Gen. Chem.], 1999, vol. 69, iss. 3, pp. 510-511 (in Russ.).