Koordinationsverbindungen des Trimethylzinn(IV)-di(fluorsulfonyl)amids: Ionische Komplexe mit einzähnigen Neutralliganden

Polysulfonylamines. CXIII. Coordination Compounds Derived from Trimethyltin(IV) Di(fluorosulfonyl)amide: Ionic Complexes with Monodentate Uncharged Ligands Me₃SnN(SO₂F)₂ reacts with two equivalents of the appropriate ligands to give the coordination compounds [Me₃Sn(L)₂]^⊕(FSO₂)₂N^⊖, where L = OSMe₂ (complex 7 , previously known), N,N′-dimethylethyleneurea (complex 8 ), OPPh₃ or OP(NMe₂)₃. Low-temperature X-ray diffraction measurements revealed 7 (triclinic, space group P 1) and 8 (monoclinic, P2₁/c) to be ionic in nature; similar structures may be surmised for the other two compounds. The (FSO₂)₂N^⊖ anion, ordered in 7 and disordered over two sites in 8 , adopts the usually observed conformation with pseudo-C₂ symmetry. The tin atoms have slightly distorted trigonal-bipyramidal coordination geometries, in which the apical positions are occupied by the oxygen atoms of the L ligands [Sn–O bond lengths for 7 : 224.9(4) and 228.1(4) pm, for 8 : 227.5(2) and 228.6(2) pm].     

Preparation and absorption spectrum studies of aromatic and alicyclic poly(amide acid) ammonium salts in water and DMF and in films

A series of ammonium salts of poly(amide acid)s (PAS) were prepared from various poly(amide acid)s (PAA) with tertiary amines. The solubility of poly(amide acid) ammonium salts prepared from PAA(PMDA/ODA) in water is related to the ion concentration of tertiary amines. In order to elucidate the influence of the chemical structures of poly(amide acid)s and poly(amide acid) ammonium salts on their absorption spectra, pyromellitic dianhydride (PMDA), 3,3′,4,4 ′-biphenyltetracarboxylic dianhydride (BPDA), and 3,3′,4,4 ′-benzophenonetetracarboxylic dianhydride (BTDA) were chosen to react with p-phenylenediamine (PDA) and (4,4′-diaminodicyclohexyl)methane (DCHM) to give three kinds of aromatic PAAs and three kinds of alicyclic PAAs. The corresponding PASs were prepared by the reaction of PAAs with triethanolamine (TEA). Their ultraviolet–visible (UV–vis) absorption spectra were investigated compared to those of model compounds. A transparent film without absorption above 320 nm was obtained for PAS(PMDA/DCHM). The difference in absorption spectra of PAS(PMDA/PDA) from that of PAS(PMDA/DCHM) can be related to the existence of intra- and intermolecular charge transfer (CT) for PAS(PMDA/PDA). The absorption spectra of PASs with PDA in films are red shifted compared to those of corresponding PAAs in films, while the absorption spectra of PASs in water are blue shifted compared to those of corresponding PAAs in DMF. No differences in the absorption spectra of PAAs and PASs were found in DMF/H₂O (9/1) mixed solvent. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1329–1340, 1998     

Relaxation behavior of aliphatic-aromatic poly(ether amide)s as revealed by dynamic mechanical and dielectric methods

The mechanical and dielectric relaxation of a set of aromatic-aliphatic polyamides containing ether linkages have been examined as a function of temperature (−140 to 190°C) and frequency (3 to 10⁶ Hz). The polymers differ in the orientation (meta and para) of the aromatic rings, in the length of the aliphatic chain, and in the number of ether linkages per repeating unit. Dynamic mechanical experiments showed three main relaxation peaks related to the glass transition temperature of the polymers (α relaxation), the subglass relaxations associated to the absorbed water molecules (β) and to the motion of the aliphatic moieties (γ). Dielectric experiments showed two subglass relaxation processes (β and γ) that correlates with the mechanical β and γ relaxations, and a conduction process (σ) above 50°C that masks the relaxation associated to the glass transition. A molecular interpretation is attempted to explain the position and intensity of the relaxation, studying the influence of the proportion of para- or meta- oriented phenylene rings, the presence of ether linkages and the length of the aliphatic chain. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 457–468, 1997     

Synthesis of telechelic oligostyrenes by the ozonoloysis of poly(styrene-stat-butadiene): Protection of styrene units against ozone attack by the use of Di-N-alkyl amides as sacrificial ozone scavengers

Polystyrene and a poly(styrene-stat-butadiene) have been reacted with ozone in various solvents to establish the conditions necessary for the production, from the latter, of telechelic oligostyrenes having high and controllable end group functionalities. Polymeric ozonides produced by ozonolysis of poly(styrene-stat-butadiene)s, on workup with sodium borohydride or zinc/acetic acid, give dihydroxy- or dialdehyde-ended oligostyrenes, respectively. Workup with borane gives oligomers with a mixture of hydroxy and aldehyde end groups. Oxidative workup with selenium dioxide/hydrogen peroxide yields carboxylic acid-ended oligostyrenes. Workup with polymer-supported reducing or oxidizing agents was less successful. It is shown that side reactions associated with the synthesis of telechelic oligostyrenes by the ozonolysis route, i.e., attack at the α position and possibly also on the phenyl rings of the styrene units, can be minimized by the use of N-dialkyl amides, particularly dimethylacetamide, as sacrificial ozone scavengers. © 1996 John Wiley & Sons, Inc.     

New Deoxycholic Acid Derived Tyrosyl-DNA Phosphodiesterase 1 Inhibitors Also Inhibit Tyrosyl-DNA Phosphodiesterase 2

A series of deoxycholic acid (DCA) amides containing benzyl ether groups on the steroid core were tested against the tyrosyl-DNA phosphodiesterase 1 (TDP1) and 2 (TDP2) enzymes. In addition, 1,2,4- and 1,3,4-oxadiazole derivatives were synthesized to study the linker influence between a para-bromophenyl moiety and the steroid scaffold. The DCA derivatives demonstrated promising inhibitory activity against TDP1 with IC₅₀ in the submicromolar range. Furthermore, the amides and the 1,3,4-oxadiazole derivatives inhibited the TDP2 enzyme but at substantially higher concentration. Tryptamide 5 and para-bromoanilide 8 derivatives containing benzyloxy substituent at the C-3 position and non-substituted hydroxy group at C-12 on the DCA scaffold inhibited both TDP1 and TDP2 as well as enhanced the cytotoxicity of topotecan in non-toxic concentration in vitro. According to molecular modeling, ligand 5 is anchored into the catalytic pocket of TDP1 by one hydrogen bond to the backbone of Gly458 as well as by π–π stacking between the indolyl rings of the ligand and Tyr590, resulting in excellent activity. It can therefore be concluded that these derivatives contribute to the development of specific TDP1 and TDP2 inhibitors for adjuvant therapy against cancer in combination with topoisomerase poisons.