Reactions of cyclochlorotriphosphazatriene with 1-amino-2-propanol. Calorimetric and spectroscopic investigations of the derived products

Year 2018, , 1033 - 1047, 01.06.2018

Murat Tuna , Sedat Türe Rafig Gurbanov

https://doi.org/10.16984/saufenbilder.384736

Abstract

Reactions of hexachlorocyclotriphosphazatriene,
N₃P₃Cl₆ (1)
with 1-amino-2-propanol (2), in
(1:1:2, 1:2:4 and 1:3:6) mole ratios, in excess of NaH, in THF and acetonitril solutions
yield a total of 6 novel products:one
mono-open chain, N₃P₃Cl₅[HN-CH₂-CH(CH₃)-OH]
(3); one monospiro,  N₃P₃Cl₄[O-CH(CH₃)-CH₂-NH]
(4); one trans bis-open chain, N₃P₃Cl₄[HN-CH₂CH(CH₃)-OH]₂
(5); one dispiro, N₃P₃Cl₂[O-HC(CH₃)-CH₂-NH]₂
(7); one tri-open chain, N₃P₃Cl₃[HN-CH₂CH(CH₃)-OH]₃
(6); and one tri-spiro, N₃P₃[O-HC(CH₃)-CH₂-NH]₃(8) derivatives.These compounds have
interesting structural aspects as well as physical properties. Their structures
were established by elemental analysis, TL-MS, ³¹P and ¹H
NMR spectral data. Stability constants were determined
using a simple potentiometric titration. For evaluation of melting behavior
and purity of derivatives (7) and (8), thermal transition peaks and their
corresponding enthalpies were determined via DSC technique. Spectroscopic
data, product types and relative
yields are compared with those of the previously investigated derivatives of N₃P₃Cl₆
(1) with aliphatic difunctional reagents.

Keywords

Hexachlorocyclotriphosphazene, 1-amino-2-propanol, spiro compounds, open chain compounds

References

• [1 ] S. B. Lee, S. C. Song, J. Il Jin, and Y. S. Sohn, “Thermosensitive cyclotriphosphazenes [9],” Journal of the American Chemical Society, vol. 122, no. 34. pp. 8315–8316, 2000. [2 ] G. Peris and S. J. Miller, “Catalysis: Triumph of a chemical underdog,” Nature, vol. 452, no. 7186. pp. 415–416, 2008. [3 ] H. R. Allcock and S. Kwon, “An Ionically Cross-Linkable Polyphosphazene: Poly[bis(carboxylatophenoxy)phosphazene] and Its Hydrogels and Membranes,” Macromolecules, vol. 22, no. 1, pp. 75–79, 1989. [4 ] H. R. Allcock and M. L. Turner, “Ring Expansion and Polymerization of Transannular Bridged Cyclotriphosphazenes and Their Spirocyclic Analogues,” Macromolecules, vol. 26, no. 1, pp. 3–10, 1993. [5 ] H. R. Allcock and G. K. Dudley, “Lower critical solubility temperature study of alkyl ether based polyphosphazenes,” Macromolecules, vol. 29, no. 4, pp. 1313–1319, 1996 [6 ] D. B. Davies et al., “Chiral configurations of cyclophosphazenes,” J. Am. Chem. Soc., vol. 122, no. 50, pp. 12447–12457, 2000. [7 ] P. I. Richards and A. Steiner, “Cyclophosphazenes as Nodal Ligands in Coordination Polymers,” Inorg. Chem., vol. 43, no. 9, pp. 2810–2817, 2004. [8 ] H. R. Allcock and E. C. Kellam, “Incorporation of cyclic phosphazene trimers into saturated and unsaturated ethylene-like polymer backbones,” Macromolecules, vol. 35, no. 1, pp. 40–47, 2002. [9 ] M. Breza, “The electronic structure of planar phosphazene rings,” Polyhedron, vol. 19, no. 4, pp. 389–397, 2000. [10 ] A. B. Chaplin, J. A. Harrison, and P. J. Dyson, “Revisiting the electronic structure of phosphazenes,” Inorg. Chem., vol. 44, no. 23, pp. 8407–8417, 2005. [11 ] R. C. Haddon, “Theoretical study of the cyclotriphosphazenes importance of phosphorus d orbitals,” Chem. Phys. Lett., vol. 120, no. 4–5, pp. 372–374, 1985. [12 ] H. R. Allcock, M. L. Turner, and K. B. Visscher, “Synthesis of transannular- and spiro-substituted cyclotriphosphazenes: x-ray crystal structures of 1,1-[N3P3(OCH2CF3)4{O2C12H8}], 1,3-[N3P3(OCH2CF3)4{O2C12H8}], 1,1-[N3P3(OCH2CF3)4{O2C10H6}], and 1,3-[N3P3(OCH2CF3)4}O2C10H6}],” Inorg. Chem., vol. 31, no. 21, pp. 4354–4364, 1992. [13 ] H. R. Allcock, “Recent advances in phosphazene (phosphonitrilic) chemistry,” Chem. Rev., vol. 72, no. 4, pp. 315–356, 1972. [14 ] H. R. Allcock, J. S. Rutt, and M. Parvez, “Synthesis of Cyclic Phosphazenes with Isothiocyanato, Thiourethane, and Thiourea Side Groups: X-ray Crystal Structure of N3P3(NMe2)3(NCS)3,” Inorg. Chem., vol. 30, no. 8, pp. 1776–1782, 1991. [15 ] C. W. Allen, “Regio- and Stereochemical Control in Substitution Reactions of Cyclophosphazenes,” Chem. Rev., vol. 91, no. 2, pp. 119–135, 1991. [16 ] E. E. Ilter et al., “Phosphorus-nitrogen compounds. 14. Synthesis, stereogenism, and structural investigations of novel N/O spirocyclic phosphazene derivatives,” Inorg. Chem., vol. 46, no. 23, pp. 9931–9944, 2007. [17 ] K. Muralidharan, P. Venugopalan, and A. J. Elias, “Ansa versus spiro substitution of cyclophosphazenes: Is fluorination essential for ansa to spiro transformation of cyclophosphazenes?,” Inorg. Chem., vol. 42, no. 10, pp. 3176–3182, 2003. [18 ] A. J. Elias, B. Twamley, and J. M. Shreeve, “Syntheses and Experimental Studies on the Relative Stabilities of Spiro, Ansa , and Bridged Derivatives of Cyclic Tetrameric Fluorophosphazene,” pp. 2120–2126, 2001. [19 ] ChemicalComputingGroupInc., “Molecular Operating Environment (MOE),” Sci. Comput. Instrum., vol. 22, no. 1, p. 32, 2004. [20 ] D. J. Lingley, R. A. Shaw, M. Woods, and S. S. Krishnamurthy, “Studies of phosphazenes. part vi. 1 the preparation of the isomeric tetrachlorobis-isopropylaminocyclotriphosphazatrienes,” Phosphorus Sulfur Relat. Elem., vol. 4, no. 3, pp. 379–382, 1978. [21 ] S. S. Krishnamurthy, K. Ramachandran, and M. Woods, “Studies of Phosphazenes, Part Xi. Syntheses and Structures of Bis(Primary Amino)Hexachlorocyclotetraphosphazenes and Their Dimethylamino Derivatives,” Phosphorus Sulfur Relat. Elem., vol. 9, no. 3, pp. 323–328, 1981. [22 ] S. Beşli et al., “Crystallographic proof of double Walden inversion in nucleophilic substitution reactions of macrocyclic cyclotriphosphazene derivatives,” Eur. J. Inorg. Chem., no. 5, pp. 959–966, 2005. [23 ] S. Beşli, S. J. Coles, D. B. Davies, M. B. Hursthouse, A. Kiliç, and R. a Shaw, “A spiro to ansa rearrangement in cyclotriphosphazene derivatives.,” Dalton Trans., no. 26, pp. 2792–2801, 2007. [24 ] D. Davarci, S. Beşli, and F. Yuksel, “Reactions of cyclotriphosphazene with 1,6-diaminohexane and 1,8-diaminooctane: Mono-ansa, double- and triple-bridged derivatives,” Polyhedron, vol. 68, pp. 10–16, 2014. [25 ] S. Beşli, S. J. Coles, D. Davarci, D. B. Davies, and F. Yuksel, “Effect of chain length on the formation of intramolecular and intermolecular products: Reaction of diols with cyclotriphosphazene,” Polyhedron, vol. 30, no. 2, pp. 329–339, 2011. [26 ] K. K. Jin, U. S. Toti, R. Song, and S. S. Youn, “A macromolecular prodrug of doxorubicin conjugated to a biodegradable cyclotriphosphazene bearing a tetrapeptide,” Bioorganic Med. Chem. Lett., vol. 15, no. 15, pp. 3576–3579, 2005. [27 ] Y. J. Jun et al., “Thermoresponsive micelles from oligopeptide-grafted cyclotriphosphazenes,” Angew. Chemie - Int. Ed., vol. 45, no. 37, pp. 6173–6176, 2006. [28 ] P. Castera et al., “An answer to the SPIRO versus ANSA dilemma in cyclophosphazenes. Part VII. Neither SPIRO nor ANSA: the BINOdicyclotriphosphazenes, N3P3Cl5 [HN(CH2)nNH] Cl5P3N3,” Inorganica Chim. Acta, vol. 108, no. 1, pp. 29–33, 1985. [29 ] X. Q. Sournies, F., Labarre, J. F., Spreafico, F., Filippeschi, S., & Jin, “Atempts at the production of more selective antitumourals part ii. The antineoplastic activity of cyclophosphazenes linked to spermine, vol. 147, pp. 161–173, 1986. [30 ] H. Alkubaisi, H. G. Parkes, and R. A. Shaw, “Phosphorus-nitrogen compounds. Part 58. The reactions of hexachlorocyclotriphosphazatriene with ethane-, 1,3-propane- and 1,4-butane-diols. Spiro, ansa, bridged and dangling derivatives and their 31P and 1H nuclear magnetic resonance spectra,” Heterocycles,vol. 28, no. 1, pp. 347–358, 1989. [31 ] I. Porwolik-Czomperlik, K. Brandt, T. A. Clayton, D. B. Davies, R. J. Eaton, and R. A. Shaw, “Diastereoisomeric singly bridged cyclophosphazene-macrocyclic compounds,” Inorg. Chem., vol. 41, no. 19, pp. 4944–4951, 2002. [32 ] (a) El Murr, N.; Lahana, R.; Labarre, J. F.; Declercq, J. P., “Phosphorus-Nitrogen compounds. Spectroscopic investigation of cyclophosphazenes” J Mol Struct, 117, 73-85, 1984. (b) J. F. Labarre,. “Spectroscopic investigation of cyclophosphazenes,”TopCurrChem, 129, 173–230, 1985. [33 ] (a) R. A. Shaw, “The Phosphazenes–Structural Parameters and Their Relationships To Physical and Chemical Properties,” Phosphorous Sulfur Relat. Elem., vol. 28, no. 1–2, pp. 99–128, 1986. (b) R. A. Shaw, "The reactions of phosphazenes with difunctional and polyfunctional nucleophilic reagents, "Phosphorus Sulfur and Silicon and the Related Elements, vol. 45, no. 1-2, pp, 103-136, 1989. [34 ] H. R. Allcock, U. Diefenbach, and S. R. Pucher, “New Mono- and Trispirocyclotriphosphazenes from the Reactions of (NPCl2)3 with Aromatic Ortho Dinucleophiles,” Inorg. Chem., vol. 33, no. 14, pp. 3091–3095, 1994. [35 ] K. Brandt et al., “Host-guest complex dependent regioselectivity in substitution reactions of chlorocyclotriphosphazene-containing PNP-crowns with alkylenediamines,” J. Am. Chem. Soc., vol. 119, no. 5, pp. 1143–1144, 1997. [36 ] S. Ture.Phosphorus-nitrogen compounds: Reinvestigation of the reactions of hexachlorocyclotriphosphazene with 1,4-butane- and 1,6-hexane-diols—NMR studies of the products, ”Phosphorous Sulfur Relat. Elem., vol.191, no. 8, pp. 1174-1182, 2016. [37 ] C. Plato and A. R. Glasgow, “Differential Scanning Calorimetry as a General Method for Determining the Purity and Heat of Fusion of High-Purity Organic Chemicals. Application to 95 Compounds,” Anal. Chem., vol. 41, no. 2, pp. 330–336, 1969. [38 ] R. B. Cassel and R. Behme, “A DSC method to determine the relative stability of pharmaceutical polymorphs,” Am. Lab., vol. 36, no. 16, pp. 0–2, 2004. [39 ] G. Knothe and R. O. Dunn, “A Comprehensive Evaluation of the Melting Points of Fatty Acids and Esters Determined by Differential Scanning Calorimetry,” J Am Oil Chem Soc, vol. 86, pp. 843–856, 2009. [40 ] Particle Analytical, “Differential Scanning Calorimetry (DSC) theory.” [Online]. Available: http://particle.dk/methods-analytical-laboratory/dsc-differential-scanning-calorimetry-2/dsc-theory/. [Accessed: 16-Nov-2017]. [41 ] R. Gurbanov and F. Yıldız, “Molecular profile of oral probiotic bacteria to be used with functional foods,” J. Food Heal. Sci., vol. 3, pp. 117–131, 2017.