Krystyna Brandt

AIDS-related lymphoma screen results and molecular structure determination of a new crown ether bearing aziridinylcyclophosphazene, potentially capable of ion-regulated DNA cleavage action

The tetraaziridinyl PNP-lariat ether has been tested in the in vitro disease-oriented antitumor screen and evaluated further in an investigational AIDS-related lymphoma screen in vitro. This compound shows remarkable cytostatic activity. The crystal and molecular structure has been determined. The PNP-lariat ether has a pseudo-mirror plane perpendicular to the ring plane. The crown ether has an internal pseudo-threefold axis of symmetry. The so-called macrocyclic CC shortening effect is observed in the crown ether. All crown ether oxygen atoms are directed toward the interior of the ring and exist in an almost ideal envelope conformation. The cyclophosphazene ring is distorted from planarity and all PN bond lengths within the ring are equal with the mean value being 1.588(3) A.

NEW DIOXYTETRAETHYLENEOXY MACROCYCLIC CYCLOPHOSPHAZENE DERIVATIVES

Abstract A series of macrocyclic cyclophosphazene containing derivatives of mono-ansa, mono-spiro, spiro-ansa and bis-ansa structure together with polymeric materials have been obtained by the reaction of hexachlorocyclotriphosphazene with tetraethylene glycol in the presence of sodium hydride. Structure determination was based on mass and 31P NMR spectral analysis. The formation of macrocyclic compounds points to a template effect being operative during substitution. The structure of the mono-ansa compound has been confirmed by an X-ray diffraction study. Crystals are triclinic, P 1 , a=7.797(1), b=10.705(1), c=12.336(1), A, α=88.74(1), β=72.404(7), γ=72.15(1)°, Z=2 at 130 K. The refinement converged to R=0.034 for 3434 unique reflections (I ⩾ 2.5σ(I)) and 273 parameters. The basic structure consists of an N3P3 six-membered ring in which two different P atoms are coupled to an O(CH2CH2O)4 chain, forming a 16-membered diphosphaza crown ether.

Ion Flotation of Zinc(II) and Cadmium(II) in the Presence of Side-Armed Diphosphaza-16-Crown-6 Ethers

Competitive flotation of zinc(II) and cadmium(II) ions from dilute aqueous solutions by side-armed lariat ether-type derivatives of diphosphaza-16-crown-6 ethers in the presence of nonylphenol nonylethylene glycol ether as the non-ionic foaming agent has been investigated. The influence of the type of group attached to the PNP-lariat ether molecule on the selectivity and efficiency of Zn(II) and Cd(II) ion flotation is studied. An effect of alkali metal cations, i.e., Li+ and Na+, on Cd(II) ion-flotation removal is also reported. It was shown that the removal of Cd2+ increases with increase of pH values and decreases with alkali metal cations concentration increase in aqueous solutions. The correlation between selectivity coefficients of Cd(II)/Zn(II) and pH of aqueous solution as well as molar intrinsic volume and hydrophilic–lipophilic balance of studied ethers was found.

SYNTHESIS AND CHARACTERIZATION OF NEW 1,1′,3,3′,5,5′-HEXACHLORO-2,4,6, 1λ5,3λ5,5λ5-TRIAZATRIPHOSPHORINE SPIRO-[ARYLENEDIOXYI-DERIVATIVES

Abstract Hitherto reported methods of substitution of 1,1′,3,3′,5,5′-hexachloro-2,4.6, 1λ5,3λ5,5λ5-triazatriphosphorine (1) with 2,2′-dihydroxy-1,1′-biphenylene (2) enabled exclusively the preparation of trisspiro-derivatives, it means fully substituted 1. We have found that when the reaction of 1 and 2 is carried out in bisolvent system containing THF/H2O or C6H5CI/H2O the partial substitution is possible resulting in the corresponding mono- and bisspiro-[2,2′-dioxybiphenyl-l,1′] derivatives of 1. An efficient method of preparation of novel compounds: 1,1′-spir0-[2,2′-dioxybiphenyl-l,1′]-3,3′,5,5′-tetrachloro-2,4,6, 1λ5,3λ5,5λ5-triazatripho∼phorine (3) and 1.1′,3,3′-bisspiro-[2,2′-dioxybiphenyl-l,1′]- 5,5′-dichloro-2,4,6, 1λ5,3λ5,5λ5-triazatriphosphorine (4) is presented. The dependence of the degree of substitution on the reaction conditions is discussed. In order to ascertain the proposed structures of the obtained compounds: 3 and 4 (Scheme 1) the corresponding phenoxy and 1-aziridinyl derivatives hav...

Change of the crown ether geometry by complexation in tetrapyrrolidinyl PNP-lariat ether. Crystal structure of the complex of tetrapyrrolidinyl PNP-lariat ether with sodium iodide

The crystal and molecular structure of the title compound, C24H50IN7NaO6P3, crystallizing in P1 space group has been determined by X-ray crystallography. The oxygen atoms of the crown ether exist in an almost ideal envelope conformation. The inorganic cyclophosphazene P3N3 ring has a non-planar envelope conformation. All endocyclic PN bond lengths are equal within experimental error with the mean value of 1.585(5) A. The Na+ ion is coordinated by oxygen atoms from the crown ether and the water molecule but not by the cyclophosphazene nitrogen atom. The OPNPO part of the 16-membered ring is flexible. The crown ether part of the 16-membered ring adopts approximately D3d symmetry. Complex mean cavity radii are close to effective ionic radii. There is no coordination bond between nitrogen and metals with effective ionic radii smaller than 2.3 A.

New Molecular Receptors with Cyclophosphazene Subunits: Synthesis, Reactivity, and Structure-Property Relationships

A series of hydrophopic ( 2 and 3) and new hydrophilic ( 4– 7) molecular receptors of the PNP-lariat ether with tetra-substituted cyclotriphosphazene subunits have been prepared by the complete nucleophilic substitution of chlorine atoms in the reactive PNP-crown precursor 1 with the respective sodium cation-paired oxyanions (phenoxy → 2, β-naphthoxy → 3, and methoxytrioxyethylenoxy → 4) and aliphatic amines (n-propylamine → 5 aziridine → 6, and pyrrolidine → 7). Their structures were established by MS and 31P NMR spectroscopy and their metal ion complexing properties tested by a TLC method. Comparison of the complexation behaviour for ligands 1– 7 shows that the affinity for particular cations is strongly substituent-dependent and, in general, is significantly enhanced by cooperation of the side arm donor atoms (O or N) with the parent PNP-crown structure in the binding process. The remarkable affinity of some ligands for selected cations, in particular lithium, cesium, and silver ions, is interpreted in terms of structure-property relationships.

Structure of the tetrabutylammonium salt of 2,4,4,6,6-pentachloro-1,3,5,2λ5,4λ5,6λ5-triazatriphosphorinine 2-oxide

[N(C4H9)4][N3P3C150], Mr--- 570.67, monoclinic, P2Jc, a=10.184(2), b=18.072(3), c = 16.448 (2) A, fl = 106.88 (2) °, V= 2896-8 (9) A 3, Z = 4, Dx = 1.308 g cm -3, A(Mo K~) = 0-71073 A, /z = 6-8 cm-i, F(000) = 1192, T = 298 K, RF = 0.082, wR = 0.069 for 2089 unique observed reflections with I >_ 1.5tr(/) and 263 parameters. The inorganic ring skeleton is nearly flat, tending somewhat to a crown conformation. The P--N bond lengths (mean values) are: N--P(OC1) 1.606 (5) A and N--P(C12) 1.540 (5), 1.58 (1) A.

Structure–alkali metal cation complexation relationships for macrocyclic PNP-lariat ether ligands

Water-insoluble, mono- and diarmed PNP-lariat ethers containing various aryloxy and regioisomerically-positioned binaphthylylenedioxy substituents linked to the phosphorus atoms of the cyclophosphazene ring via oxygen atoms are synthesized by regioselective, sodium ion-assisted arylolysis of tetrachloro-16-PNP-6 crown ether 1. Heterogeneously-substituted, mixed aryloxy-amino PNP-lariat ethers and bis-lariat ethers with two different substituents linked to the PNP-macrocycle via an oxygen and a nitrogen atom are prepared by stepwise arylolysis and aminolysis reactions of 1. The alkali-metal cation complexation behavior of the PNP-lariat ethers is evaluated in solvent polymeric membrane electrodes. The PNP-lariat and bis-lariat ethers exhibit pronounced selectivity for large alkali metal cations (Rb+ and Cs+) over small ones (Li+ and Na+). The selectivity is influenced by the configuration of the crown ether ring and the number of oxygen donor atoms in the ligand. For some PNP-lariat ethers, evidence for formation of 2 : 1 (ligand–metal ion) complexes with Rb+ and Cs+ is provided by ESI-MS.

Synthesis, Crystal and Molecular Structure of Tetrapyrrolidinyl PNP-lariat Ether Complex with Ki(H2O)2 Monohydrate

The crystal and molecular structure of the title compound, C24H50N7O8IKP3 crystallizing in P21/c space group has been determined. The oxygen atoms of the crown ether exist in an almost ideal envelope conformation. The inorganic cyclophosphazene ring P3N3 is slightly deviated from planarity. All endocyclic P-N bond lengths are equal within experimental error with the mean value 1.585(5) Å. The K+ ion is coordinated by oxygen atoms from the crown ether and two water molecules but not by the cyclophosphazene nitrogen atom.

Comparison of the electronic absorption spectra of the isomeric 1,1′- and 2,2′-binaphthyl spiro [cyclophosphazene] derivatives

Abstract It has been found that the u.v.-spectrum of the monospiro [(2,2′-dioxybinaphthyl-1,1′) cyclophosphazene] ( 3 ) closely resembles those of the other previously described 7-membered 2,2′-bridged 1,1′-binaphthyl derivatives. An hitherto unreported effect of the associated influence of α-substitution, β-coupling and the next cyclization on the u.v. absorption of naphthalene chromophore has been shown by the comparison of the electronic spectra of 1-naphthol ( 5 ), 1,1′-dihydroxybinaphthyl-2,2′ ( 6 ) and monospiro [(1,1′-dioxybinaphthyl-2,2′) cyclophosphazene] ( 7 ). Exclusively strong resonance interaction between the conjugated naphthalene rings was evidenced for 7 .