Structural Features of Naphthophosphacyclophanes Based on Dihydroxynaphthalenes

The computer simulation of the synthesized cyclophane-like macrocyclic systems based on 1,6-, 2,6-, and 2,7-dihydroxynaphthalenes and full amides of phosphorus acid with different substituents at the phosphorus atom is carried out. The equilibrium geometry of molecules of synthesized "uniform" naphthophosphacyclophanes was evaluated using the semi-empirical method PM3 and the quantum-chemical ab initio HF(3-21G) calculations. Based on correlation of the data from the ¹H and ³¹P NMR spectroscopy (as well as the ROESY two-dimensional spectroscopy) and the calculation results of the semi-empirical method PM3, optimal configurations of the synthesized naphthophosphacyclophanes are determined. It is shown that the mutual disposition of aromatic fragments depends on structural features of the initial naphthodiol and is independent of substituents at the phosphorus atom. It is noted that in all cases regardless of the synthetic pathway, the formation of the single configuration of macrocyclic structure occurs, while a change in the phosphorus center configuration results in the insignificant distortion of a general configuration of the molecule.

References

[1] Nifantyev E.E., Slitikov P.V., Rasadkina E.N. Synthesis of arylenephosphamacrocycles using tri- and pentavalent phosphorus compounds. Uspekhi khimii [Russ. Chem. Rev., 2007, 76 (4), 327-338], 2007, vol. 76, no. 4, pp. 362-374 (in Russ.). DOI: 10.1070/RC2007v076n04ABEH003667.

[2] Knyazeva I.R., Burilov A.R., Pudovik M.A., Khabikher V.D. Phosphorus-containing macrocyclic compounds: synthesis and properties. Uspekhi khimii [Russ. Chem. Rev., 2013, 82 (2), 150-186], 2013, vol. 82, no. 2, pp. 150-186 (in Russ.). DOI: 10.1070/RC2013v082n02ABEH004296.

[3] Nifant’ev E.E., Rasadkina E.N., Yankovich I.V., Vasyanina L.K., Belskiy V.K. Stash A.I. Heterocycles with alternating residues of phosphorus acids and metaphenyl fragments. Zhurnal Obshchei Khimii [Russ. J. Gen. Chem., 1999, 69 (1), 32-38], 1999, vol. 69, i. 1, pp. 36-42 (in Russ.).

[4] Nifant’ev E.E., Suvorkin S.V., Rasadkina E.N., Selutina O.V., Shishin A.V. Effect of isopropyl group compounds in phosphorylation of phenols by amides of phosphorous acid. Zhurnal Obshchei Khimii [Russ. J. Gen. Chem., 1999, 69 (8)], 1999, vol. 69, i. 8, pp. 1263-1266 (in Russ.).

[5] Nifant’ev E.E., Rasadkina E.N., Evdokimenkova Yu.B. Phosphacyclophanes derived from hydroquinone and 4,4’-dihydroxybiphenyl. Zhurnal Obshchei Khimii [Russ. J. Gen. Chem., 2001, 71 (3), 366-372], 2001, vol. 71, i. 3, pp. 401-408 (in Russ.). DOI: 10.1023/A:1012357001662.

[6] Nifant’ev E.E., Rasadkina E.N., Suvorkini S.V., Gusev D.V. Preparative method of synthesis of phosphoramidite macroheterorings derived from 2,2’-Bis(4-hydroxyphenyl)propane and related phenols. Zhurnal Obshchei Khimii [Russ. J. Gen. Chem., 2001, 71 (8), 1325-1326], 2001, vol. 71, i. 8, pp. 1403-1404 (in Russ.). DOI: 10.1023/A:1013262120747.

[7] Rasadkina E.N., Nifant’ev E.E. Dioxaphosphacyclophanes - new type of doubledeck systems. Zhurnal Obshchei Khimii [Russ. J. Gen. Chem., 1999, 69 (3)], 1999, vol. 69, i. 3, pp. 510-511 (in Russ.).

[8] Nifant’ev E.E., Rasadkina E.N., Evdokimenkova Yu.B., Vasyanina L.K., Belskiy V.K., Stash A.I. Dioxaphosphacyclanes. Synthesis and chemical properties. Zhurnal Obshchei Khimii [Russ. J. Gen. Chem., 2001,71 (2), 179-187], 2001, vol. 71, i. 2, pp. 203-211 (in Russ.). DOI: 10.1023/A:1012378817167.

[9] Nifant’ev E.E., Rasadkina E.N., Evdokimenkova Yu.B. Synthesis of cavity systems by cyclophosphorylation of 1,7-dihydroxynaphthalene with phosphorous triamides. Izv. An. Ser. Khim. [Russ. Chem. Bull., 2001, 50 (5), 923-924], 2001, no. 5, pp. 883884 (in Russ.). DOI: 10.1023/A:1011392017095.

[10] Rasadkina E.N., Slitikov P.V., Mel’nik M.S., Bel’skii V.K., Stash A.I., Nifant’ev E.E. 2,6- and 1,6-dihydroxynaphthalenes in the synthesis of phosphacyclophanes. Zhurnal Obshchei Khimii [Russ. J. Gen. Chem., 2004, 74 (7), 1080-1086], 2004, vol. 74, i. 7, pp. 1170-1176 (in Russ.). DOI: 10.1023/B:RUGC.0000045868.37162.87.

[11] Nifant’ev 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] Rasadkina E.N., Slitikov P.V., Mel’nik M.S., Nifant’ev 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.

[13] Rasadkina E.N., Slitikov P.V., Pechkina M.P., Vasyanina L.K., Stash A.I., Nifant’ev E.E. 1,3-Dihydroxynaphthalene in the synthesis of phosphorus-containing macroheterocycles. Zhurnal Obshchei Khimii [Russ. J. Gen. Chem., 2005, 75 (12), 1910-1918], 2005, vol. 75, i. 12, pp. 2000-2008 (in Russ.). DOI: 10.1007/s11176-006-0013-3.

[14] Slitikov P.V., Rasadkina E.N., Korunova Yu.A., Vasyanina L.K., Nifant’ev E.E. Phosphomacrocyclic systems based on 2,2’-dihydroxy-1,1’-dinaphtylmethane. Zhurnal Obshchei Khimii [Russ. J. Gen. Chem., 2010, 80 (5), 920-926], 2010, vol. 80, i. 5, pp. 750-756 (in Russ.). DOI: 10.1134/S1070363210050099.

[15] Slitikov P.V., Evdokimenkova Yu.B.,. Rasadkina E.N, Vasyanina L.K., Nifant’ev E.E. Synthesis and characterization of phosphamacrocycles based on 2,7-dihydroxynaphthalene. Macroheterocycles, 2011, vol. 4, no. 4, pp. 311-323 (in Russ.). DOI: 10.6060/mhc2011.4.07.

[16] Slitikov P.V., Rasadkina E.N., Vasyanina L.K., Nifant’ev 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.

[17] Nifant’ev E.E., Rasadkina E.N., Petrov A.V. Phosphacyclophanes derived from anthracene-2,6-diol. Zhurnal Obshchei Khimii [Russ. J. Gen. Chem., 2005, 75 (4), 660-661], 2005, vol. 75, i. 4, pp. 698-699 (in Russ.). DOI: 10.1007/s11176-005-0292-0.

[18] Rasadkina E.N., Petrov A.V, Nifant’ev E.E. Phosphorylation and cyclophosphorylation of 1,4-diacetoxyanthracene and dianthrone. Zhurnal Obshchei Khimii [Russ. J. Gen. Chem., 2007, 77 (2), 241-247], 2007, vol. 77, i. 2, pp. 268-274 (in Russ.). DOI: 10.1134/S1070363207020090.

[19] Nifant’ev E.E., Petrov A.V, Stash A.I., Rasadkina E.N. Antracenediols in the synthesis of phosphacyclophanes. Phosphorus, sulfur and silicon, 2007, vol. 182, по. 6, pp. 1413-1424. DOI: 10.1080/10426500701196481.

[20] Slitikov P.V., Rasadkina E.N., Vasyanina L.K., Nifant’ev E.E. The cyclic bisamidophosphites based on 1,6-dihydroxynaphthalene. Izv. AN. Ser. Khim. [Russ. Chem. Bull., 2014, 63 (9)], 2014, no. 9, pp. 362-368 (in Russ.).

[21] Steed W.J., Atwood J.L. Supramolecular chemistry. John Wiley & Sons, Ltd, 2000. 772 p. (Russ. ed.: Steed W.J., Atwood J.L. Supramolekulyarnaya khimiya]. In 2 volumes. Akademkniga Publ., 2007. 480 p.).

[22] Blank N.E., Haenel M.W. Modelle f"urEximere: Diastereomere [3.3](2,6)- und [3.3](1,5)(2,6)naphtalinophane. Chem. Ber., 1981, vol. 114, no. 4, pp. 1520-1530.