Novel quaternary ammonium borates as latent catalysts for epoxy–phenolic resins

Novel tetrabutylammonium tetrakis(substituted benzoyloxy)borate salts ( 1a – 1d ) were synthesized by the reaction of tetrabutylammonium tetraphenylborate and corresponding substituted benzoic acids. Polyaddition reactions of diglycidyl ether of bisphenol A (DGEBA) and 4,4′‐bisphenol F (44BPF) or bisphenol F (BPF‐D) with the ammonium borates were investigated as model reactions of epoxy/phenol–novolac resin systems with respect to the thermal latency and storage stability of the catalyst. The polyaddition of DGEBA/44BPF with the ammonium borates in diglyme at 150 °C for 6 h proceeded up to 84–94% conversions and gave polymers with number‐average molecular weights of 3750–5750, whereas the polyaddition at 80 °C for 6 h gave less than 9% conversions. The catalytic activity of ammonium borates 1a – 1d depended on the substituent of the phenyl group of the borates, and the order of activity was 1b (p‐OMe) > 1a (? H) > 1c (p‐NO₂) > 1d [3,5‐(NO₂)₂]. The ammonium borate catalyst with the substituent that yielded lower acidity of the corresponding substituted benzoic acid tended to reveal higher activity. In comparison with tetrabutylammonium bromide (TBAB) as a conventional ammonium salt, 1a – 1d revealed better thermal latency. The storage stability of DGEBA/BPF‐D with the ammonium borate catalysts in bulk at 40 °C was better than that with TBAB. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2689–2701, 2002     

Chiral bis(mandelato)borate salts for resolution via metathesis crystallization

Spiroborate anions have potential for crystallization or resolution and chiral bis(mandelato)borate anions can be used for the efficient resolution of a diverse range of racemic cations via diastereomeric salt formation. The syntheses, X‐ray crystal structures and solubilities of three chiral bis(mandelato)borate salts, namely poly[[aqua‐μ₃‐bis[(R )‐mandelato]borato‐lithium(I)] monohydrate], [Li(C₁₆H₁₂BO₆)(H₂O)]_n or Li[B(R‐Man)₂]·H₂O, (1), ammonium bis[(R )‐mandelato]borate, NH₄⁺·C₁₆H₁₂BO₆⁻ or NH₄[B(R‐Man)₂], (2), and tetra‐n‐butylammonium bis[(R )‐mandelato]borate, C₁₆H₃₆N⁺·C₁₆H₁₂BO₆⁻ or NBu₄[B(R‐Man)₂], (3), are reported. They all have a B_S configuration and show a reasonably well‐conserved anion geometry. The main conformational variation is the orientation of the two phenyl groups, supporting the idea that [B(Man)₂]⁻ is a semi‐rigid anion. The salts are differentially soluble in a range of solvents, meaning they could be useful as reagents for resolution via a metathesis crystallization approach.     

d‐electron count,ion‐pairing and diagonal twist angles in metallo‐bis(dithiolene) complexes

Electronic structure calculations for late transition metals coordinated by two dithiolene ligands are found to be consistent with existing structures and also predict the geometries of Ni(I) species for which no solid state structures have been reported. Of particular interest are the compounds [M(mnt)₂]^{n −} (M = Ni, Pd, and Pt with n = 1, 2, 3; M = Cu with n = 2). Calculations have been performed with and without ion‐paring with M(diglyme)⁺ (M = Li, Na, K) and R₄N⁺ (R = Me, Bu). The diagonal twist angle between two NiS₂ planes is found to depend on (i) the metal's d‐electron count, spanning from 0° (planar d⁷ and d⁸), to 42° (d⁹), to 90° (pseudo‐tetrahedral d¹⁰), and (ii) the identity of the ion‐paired cations. Calculated ion‐pairing energies are functions of the cation size and charge‐density, being larger for alkali‐metal coordinated diglyme and smaller for tetra‐alkyl ammonium cations. © 2016 Wiley Periodicals, Inc.     

Synthesis and characterization of fluoropolymers by the polyaddition of bis(epoxide)s with dicarboxylic acids and diols

The synthesis and characterization of the fluoropolymers poly 1a – 1d and poly 2a – 2d with pendant hydroxyl groups were examined. The polyaddition of bis(epoxide)s [2,2′‐bis(4‐glycidyletherphenyl)hexafluoropropane and bisphenol A diglycidyl ether] with dicarboxylic acids (tetrafluoroterephthalic acid and terephthalic acid) and diols [2,2′‐bis(4‐hydroxyphenyl)hexafluoropropane, 2,2′,3,3′,5,5′,6,6′‐octafluoro‐4,4′‐biphenol, 1,4‐bis(hexafluorohydroxyisopropyl)benzene, and 1,3‐bis(hexafluorohydroxyisopropyl)benzene] was carried out at 50–100 °C for 6–48 h in the presence of quaternary onium salts (tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylphosphonium bromide, and tetrabutylphosphonium chloride; 2.5 mol %) as catalysts in dimethyl sulfoxide, N‐methylpyrrolidone, dimethylformamide, dimethylacetamide, dioxane, diglyme, o‐dichlorobenzene, chlorobenzene, and toluene to afford the corresponding polymers, poly 1a – 1d and poly 2a – 2d , with number‐average molecular weights of 11,000–59,400 in 45–97% yields. The solubility of the obtained polymers was good, and their thermal stability might be assumed from their structures. A linear relationship was observed between the contents of the fluorine atoms and the refractive indices. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1395–1404, 2002     

Non‐Planar Lithium‐Phthalocyanine in the Double Salt (nBu4N)2[Lipc]PF6

We report the synthesis of the diamagnetic double salt bis(tetra(n‐butyl)ammonium) phthalocyanato(2‐)lithate hexafluorophosphate (nBu₄N)₂[Lipc]PF₆ [pc = phthalocyanine, nBu₄N⁺ = tetra(n‐butyl)ammonium] in dme (dme = dimethoxyethane). According to single‐crystal X‐ray diffraction structure analysis [P$\bar{1}$ , a = 8.642(2) Å, b = 12.820(3) Å, c = 15.019(3) Å, α = 83.01(3)°, β = 87.87(3)°, γ = 74.45(3)°, Z = 1, R₁ = 6.4 %], the phthalocyanine building bloc shows a substantial distortion of the macrocyclic ring from planarity. The deviation from D_4h symmetry originates from packing effects induced by the two tetra(n‐butyl)ammonium cations located above and below the macrocycle. DFT structure optimization starting from the experimental non‐planar configuration produces a fully planar complex anion [Lipc]^–.     

A rare octacoordinated mononuclear iron(III) spin‐crossover compound: synthesis,crystal structure and magnetic properties

The chemistry of transition‐metal complexes with unusually high coordination numbers has been of interest because of their application in catalytic and biological systems. Deprotonation of the ionogenic tetradentate ligand 6,6′‐bis(1H‐tetrazol‐5‐yl)‐2,2′‐bipyridine [H₂bipy(ttr)₂] in the presence of iron(III) and tetra‐n‐butylammonium bromide, [n‐Bu₄N]Br, in solution resulted in the synthesis of a rare octacoordinated anionic mononuclear complex, tetra‐n‐butylammonium bis[6,6′‐bis(tetrazol‐1‐id‐5‐yl)‐2,2′‐bipyridine]iron(III) methanol hemisolvate dihydrate, (C₁₆H₃₆N)[Fe(C₁₂H₆N₁₀)₂]·0.5CH₃OH·2H₂O or [n‐Bu₄N][Fe{bipy(ttr)₂}₂]·0.5CH₃OH·2H₂O ( 1 ), which has been structurally characterized by elemental analysis, powder X‐ray diffraction (PXRD) and single‐crystal X‐ray diffraction. In 1 , the coordination sphere of the iron(III) ion is a distorted bis‐disphenoid dodecahedron, in which the eight coordination positions are occupied by eight N atoms from two independent tetradentate [bipy(ttr)₂]^2? anionic ligands, therefore forming the anionic [Fe{bipy(ttr)₂}₂]^? unit, with the negative charge balanced by a free [n‐Bu₄N]⁺ cation. An investigation of the magnetic properties of 1 revealed a gradual incomplete spin‐crossover behaviour below 150 K.     

Effect of tetra‐n‐butylammonium bromide salt on the cationic polymerization of dimethylketene and on the thermal properties of the obtained polyketones

The cationic polymerization of dimethylketene is achieved in dichloromethane at ?30 °C, using a stoichiometric mixture of aluminum bromide (AlBr₃) and tetra‐n‐butylammonium bromide (n‐Bu₄N⁺Br^?) as initiator. Characterizations by ¹H and ¹³C NMR show that the resulting polymers have a perfect polyketonic microstructure. Capillary viscosity, DSC, and SEC analysis show that for a constant monomer/initiator ratio, polymers synthesized in the presence of tetra‐n‐butylammonium bromide are more crystalline and have better properties than those produced only with AlBr₃. Melting temperatures, inherent viscosities and average molecular weights are systematically higher. A good linearity is observed between ln (inherent viscosity) versus ln for the system with n‐Bu₄N⁺Br^?, showing a good control of the molecular weight by the initial feed ratio. The effect of this compound suggests a reversible equilibrium between active and dormant species, which limits the transfer and/or termination reactions, and enables a better control of the cationic polymerization. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1493–1499     

Bis(diisopropylammonium) thiosulfate and bis(tert‐butylammonium) thiosulfate

Two new dialkylammonium thiosulfates, namely bis(diisopropylammonium) thiosulfate, 2C₆H₁₆N⁺·S₂O₃²⁻, (I), and bis(tert‐butylammonium) thiosulfate, 2C₄H₁₂N⁺·S₂O₃²⁻, (II), have been characterized. The secondary ammonium salt (I) crystallizes with Z = 4, while the primary ammonium salt (II), with more hydrogen‐bond donors, crystallizes with Z = 8 and a noncrystallographic centre of inversion. In both salts, the organic cations and thiosulfate anions are linked within extensive N—H...O and N—H...S hydrogen‐bond networks, forming extended two‐dimensional layers. Layers are parallel to (10) in (I) and to (002) in (II), and have a polar interior and a nonpolar hydrocarbon exterior. The layered structure and hydrogen‐bond motifs observed in (I) and (II) are similar to those in related ammonium sulfates.     

Synthese und Eigenschaften von Bis(tetra(n-butyl)ammonium)-μ-carbidodi(halogenophthalocyaninato(2–)ferraten(IV)); Kristallstruktur von Bis(tetra(n-butyl)ammonium)-μ-carbidodi(fluorophthalocyaninato(2–)ferrat(IV))-Trihydrat

Synthesis and Properties of Bis(tetra(n-butyl)ammonium)μ-Carbido-di(halophthalocyaninato(2–)ferrates(IV)); Crystal Structure of Bis(tetra(n-butyl)ammonium) μ-Carbido-di(fluorophthalocyaninato(2–)ferrate(IV)) Trihydrate μ-Carbido-di(pyridinephthalocyaninato(2–)iron(IV)) reacts with tetra(n-butyl)ammonium halide (ⁿBu₄N)X) in solution (X = F) or in a melt (X = Cl, Br) to yield bis(tetra(n-butyl)ammonium μ-carbido-di(halophthalo-cyaninato(2–)ferrat(IV)). The fluoro-complex salt crystallizes as a trihydrate monoclinically in the space group P12₁/n1 with the following cell parameters: a = 15.814(1) Å; b = 22.690(5) Å; c = 25.127(3) Å; β = 98.27(1)°, Z = 4. The Fe atoms are almost in the centre (Ct) of the (N_iso)₄ planes (N_iso: isoindoline-N atom) with a Fe–Ct distance of 0.053(1) Å. The average Fe–N_iso distance is 1.939(4) Å, the Fe–(μ-C) distance 1.687(4) Å and the Fe–F distance 2.033(2) Å. The Fe–(μ-C)–Fe core is linear (179.5(3)°). The pc²-ligands are staggered (φ = 42(1)°) with a convex distortion. The asymmetric Fe–(μ-C)–Fe stretch (in cm^–1) is observed in the IR spectra at 917 (X = F), 918 (Cl) and 920 (Br) and the symmetric Fe–(μ-C)–Fe stretch at 476 cm^–1 in the resonance Raman spectra. The IR active asymmetric Fe–X stretch (in cm^–1) absorbs at 336 (X = F), 203 (Cl), 182 (Br), respectively.     

Torsional Motion in (tert‐Butyl)ammonium Hemispheraplexes: Rotational Barriers and Energy of Binding

The ADPs (ADPs=atomic anisotropic displacement parameters) from the single‐crystal X‐ray studies of nine related TBA⁺ (TBA⁺=(tert‐butyl)ammonium) hemispheraplexes are analyzed, and the results compared to the free energy of binding of this guest by the nine hosts. The lipophilic hosts (Fig. 1) were synthesized over a number of years, with increasing pre‐organization for and specificity of binding. Structural studies for six of the complexes have been published, but the remaining three structures, including those of the strongest binders of TBA⁺, are disordered and have only now been completed. New area‐detector data has been analyzed for the TBA⁺ClO complexes of 5 and of 8 at two temperatures, while the original data for 9 ?TBA⁺SCN^? has been treated with a disorder model. In addition, improved models are presented for the complexes of 6 and 7 . Methods for assessing the precision of the ADP analyses are discussed. Although most of the structures are imprecise, the TBA⁺ groups do demonstrate some of the characteristics of independent motion. The general trend in calculated libration amplitudes for the TBA⁺ group suggests that the guests with the greatest free energy of binding, and the shortest distances from N⁺ to the ligand plane, are those with the highest barriers to internal rotation.     

Pd(0)‐catalyzed polyaddition of bifunctional vinyloxiranes with 1,3‐dicarbonyl compounds: The synthesis of polymers containing hydroxy and carbonyl groups

The palladium(0)‐catalyzed polyaddition of bifunctional vinyloxiranes [1,4‐bis(2‐vinylepoxyethyl)benzene ( 1a ) and 1,4‐bis(1‐methyl‐2‐vinylepoxyethyl)benzene ( 1b )] with 1,3‐dicarbonyl compounds [methyl acetoacetate ( 4 ), dimethyl malonate ( 6 ), and Meldrum's acid ( 8 )] was investigated under various conditions. The polyaddition of 1 with 4 was carried out in tetrahydrofuran with phosphine ligands such as PPh₃ and 1,2‐bis(diphenylphosphino)ethane (dppe). Polymers having hydroxy, ketone, and ester groups in the side groups ( 5 ) were obtained in good yields despite the kinds of ligands employed. The number‐average molecular weight value of 5b was higher than that of 5a . The polyaddition of 1b and 6 was affected by the kinds of ligands employed. The corresponding polymer 7b was not obtained when PPh₃ and 1,2‐bis(diphenylphosphino)ferrocene were used. The polyaddition was carried out with dppe as the ligand and gave polymer 7b in a good yield. The molecular weight of the polymer obtained from 1b and 8 was much higher than those of polymers 5b and 7b . The polyaddition with Pd₂(dba)₃ · CHCl₃/dppe as a catalyst (where dba is dibenzylideneacetone) produced polymer 9b in a 92% yield (number‐average molecular weight = 45,600). The stereochemistries of all the obtained polymers were confirmed as an E configuration by the coupling constant of the vinyl proton. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2487–2494, 2002     

Tetra(n-butyl)ammoniumphthalocyaninato(2–)lithat-Tetrahydrofuran und Bis(tetra(n-butyl)ammonium)phthalocyaninato(2–)lithatfluorid-Hydrat; Synthese und Kristallstruktur

Tetra(n-butyl)ammonium Phthalocyaninato(2–)lithate Tetrahydrofurane and Bis(tetra(n-butyl)ammonium) Phthalocyaninato(2–)lithate Fluoride Hydrate; Synthesis and Crystal Structure Dilithiumphthalocyaninate(2–) reacts with excess tetra(n-butyl)ammonium fluoride trihydrate to yield a mixture of blue tetra(n-butyl)ammonium phthalocyaninato(2–)lithate tetrahydrofurane and bis(tetra(n-butyl)ammonium) phthalocyaninato(2–)lithate fluoride hydrate. The latter crystallizes triclinic with crystal data: a = 8.6480(1) Å; b = 12.620(2) Å; c = 14.866(5) Å; α = 82.44(2)°; β = 87.01(2)°; γ = 75.02°; space group P1 ; Z = 1. Fluoride is not coordinated to lithium. On the contrary, a double-salt is formed, which consists of alternating layers of cations and anions. This arrangement opens a cavity in the centre of the unit cell which shares statistically a fluoride and a disordered fluoride hydrate. Pure tetra(n-butyl)ammonium phthalocyaninato(2–)lithate is obtained as a tetrahydrofurane solvate by the reaction of dilithiumphthalocyaninate(2–) with tetra(n-butyl)ammonium bromide in tetrahydrofurane. The solvate crystallizes monoclinic with crystal data: a = 12.455(5) Å; b = 23.396(5) Å; c = 16.120(5) Å; β = 94.986(5)°; space group P2/c1; Z = 4.     

Synthesis and Structures of the Novel Biferrocenamine‐Based Receptor and its Voltammetric Responses to Transition Metal Ions

Reactions of formylferrocene and 1,2‐di‐(o‐aminophenoxy)ethane yield the novel bis(ferrocenyl) receptor (FcL). This compound has been characterized by IR, ¹H NMR and elemental analysis. In addition, the electrochemical behavior of FcL was investigated in detail in 0.1 M tetra‐n‐butylammonium perchlorate (TBAP) + CH₃CN by cyclic voltammetry (CV) and chronoamperometry. Its co‐ordination properties with metal ions in acetonitrile were also studied. The FcL shows a two‐wave behavior for H⁺, Cu²⁺, Zn²⁺ and Ni²⁺, but was unresponsive to Mg²⁺ and Ca²⁺. The maximum oxidation peak shift of about 250 mV was found for FcL in the presence of Cu²⁺, Zn²⁺ or Ni²⁺.     

Novel synthesis of reactive polycarbonates with pendant chloromethyl groups by the polyaddition of bis(oxetane)s with 2,2′‐bis[(4‐chloroformyl)oxyphenyl]propane

The polyaddition of 1,4‐bis[(3‐ethyl‐3‐oxetanyl)methoxymethyl]benzene with 2,2′‐bis[(4‐chloroformyl)oxyphenyl]propane was examined with quaternary onium salts as catalysts. When the polyaddition was carried out with tetrabutylphosphonium bromide in chlorobenzene at 120 °C for 24 h, the corresponding poly(alkyl aryl carbonate) with a high molecular weight (number‐average molecular weight = 16,700) was obtained in an almost quantitative yield. It was found from the ¹H NMR and ¹³C NMR spectra of the obtained polymer that the addition reaction proceeded without any side reactions, providing the polycarbonate with pendant chloromethyl groups in the side chain. The polyaddition of bis{[3‐(3‐ethyloxetanyl)]methyl}terephthalate also proceeded smoothly and gave the corresponding polycarbonate with high molecular weight in a good yield. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2304–2311, 2003     

Solvent Extraction of Ag(I) and Cu(II) with New Macrocyclic Schiff Bases

Two new macrocyclic Schiff bases (II) and (III) containing nitrogen ‐ oxygen donor atoms were synthesized by reaction between diethylene triamine or 2,2′‐(ethylenedioxy)bis(ethylamine) and the intermediate compound: 1,4‐bis(6‐methoxy‐2‐formylphenyl)‐1,4‐dioxabutane (I). Identification of these macrocyclic Schiff bases: 1,12, 15,18, 29,32 ‐ hexaaza ‐ [3,4;8,9;20,21;26,27‐tetra‐(6′‐methoxyphenyl)]‐5,8,22,25‐tetraoxa cyclo tetratriacosine‐1,11,18,28‐tetraene. (II) 1,12,21,32‐tetraaza‐[3,4;9,10;23,24;29, 30‐tetra‐(6′‐methoxyphenyl)]‐5,8,15,18,25,28,35,38‐octaoxa cyclo ‐ tetracontane‐1,11,21,31‐tetraene. (III) were determined by elemental analysis (LC‐MS), (IR) and (¹H and ¹³C‐NMR) spectroscopy. The liquid‐liquid extraction of metal picrates such as Ag⁺ and Cu²⁺ from aqueous phase to organic phase was carried out using these ligands. The effect of chloroform and dichloromethane as organic solvents over the metal picrate extractions were investigated at 25 ± 0.1 °C by using atomic absorption spectrometer.     

Pd(0)‐catalyzed polyaddition of bifunctional vinyloxiranes with phenol derivatives: The synthesis of polymers containing an allyl aryl ether moiety in the main chain

The palladium(0)‐catalyzed polyaddition of bifunctional vinyloxiranes [1,4‐bis(2‐vinylepoxyethyl)benzene ( 1a ) and 1,4‐bis(1‐methyl‐2‐vinylepoxyethyl)benzene ( 1b )] with oxygen nucleophiles such as hydroquinone and bisphenol A gave new unsaturated polyethers containing an allyl aryl ether moiety and pendant hydroxy groups. The polyaddition with 1a was largely affected by the phosphine ligands employed and the reaction temperature. The polyaddition with hydroquinone and bisphenol A was conducted at room temperature for 24 h in tetrahydrofuran in the presence of PPh₃ and gave the desired polyethers in good yields, the number‐average molecular weights (M_n) of which were 5700 and 7700, respectively. 1,2‐Bis(diphenylphosphino)ethane (dppe) was not effective in the polyaddition with 1a . The polyaddition of 1b with hydroquinone and bisphenol A gave the corresponding polyethers despite the kinds of ligands employed (PPh₃ and dppe), contrary to the polyaddition with 1a . The polyaddition of 1b with 4,4′‐biphenol was also carried out in the presence of Pd₂(dba)₃ · CHCl₃/dppe as a catalyst (where dba is dibenzylideneacetone) and afforded the expected polyether with a high M_n value (M_n = 24,900). In addition, vinyloxirane 1b could reacted with racemic 1,1′‐bi‐2‐naphthol to give the corresponding polyether in a good yield. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 476–482, 2003     

Fluorokomplexe von Platin(II): Synthese,NMR‐ und Schwingungsspektren von Tetrafluoroplatinat(II) und Difluorooxalatoplatinat(II)

Fluorine Complexes of Platinum(II): Synthesis, NMR and Vibrational Spectra of Tetrafluoroplatinate(II) and Difluorooxalatoplatinate(II) From the platinum(IV) compounds (n‐Bu₄N)₂[PtF₄(ox)] und cis‐(n‐Bu₄N)₂[PtF₂(ox)₂] on exposure to ultraviolet light at —196 °C the new platinum(II) fluorine complexes (n‐Bu₄N)₂[PtF₄] ( 1 ) and (n‐Bu₄N)₂[PtF₂(ox)] ( 2 ) are formed by elimination of a single oxalate ligand. With the synthesis of 1 the series of the tetra halogeno platinates(II) is completed now. With Cs⁺ and bis‐(triphenylphosphine)iminium(PNP⁺) as cations tetrafluoroplatinate(II) can be precipitated as pale yellow salts. Under exclusion of air all compounds are stable at —30 °C for several days, but they decompose and become black at room temperature in air within some hours. The infrared spectrum (60 K) of 1 exhibits the antisymmetric PtF stretching vibration at 515 and two deformation vibrations at 255 and 230 cm^—1. In the Raman spectrum (293 K) of (PNP)₂[PtF₄] the symmetric PtF stretching vibrations appear at 595 and 565 cm^—1. The calculated valence force constant is f_d(PtF) = 3.09 mdyn/Å. The NMR shifts are δ(¹⁹⁵Pt) = 6592 ( 1 ) and 5099 ( 2 ) and δ(¹⁹F) = —428 ( 1 ) and —393 ppm ( 2 ) with the coupling constants ¹J(PtF) = 1747 ( 1 ) and 1385 Hz ( 2 ).     

Novel synthesis of polyphosphonates by the polyaddition of bis(epoxide) with diaryl phosphonates

The polyaddition of bisphenol A diglycidyl ether (BPGE) with bis(4‐chlorophenyl) phenylphosphonate was carried out using quaternary onium salts or crown ether complexes as catalysts. When the polyaddition was performed using tetrabutylammonium chloride, tetrabutylphosphonium chloride, or 18‐crown‐6/KCl in N‐ methyl‐2‐pyrrolidone at 110°C for 48 h, the corresponding polyphosphonate with moderated molecular weights was obtained in 88–96% yields. The structure of the resulting polyphosphonate was confirmed by IR and ¹H‐NMR spectra. The polyaddition of BPGE with various diaryl phosphonates also proceeded very smoothly to produce the corresponding polyphosphonates with moderate molecular weights. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 959–965, 1999     

‘Click Synthesis’ of Some Novel Benzimidazol Oxime Ethers Containing Heterocycle Residues as Potential ß‐Adrenergic Blocking Agents

The ‘click synthesis’ of some novel O‐substituted oximes, 5a – 5j , which contain heterocycle residues, as new analogs of ß‐adrenoceptor antagonists is described (Scheme 1). The synthesis of these compounds was achieved in four steps. The formation of (E)‐2‐(1H‐benzo[d]imidazol‐1‐yl)‐1‐phenylethanone oxime, followed by their reaction with 2‐(chloromethyl)oxirane, afforded mixture of oil compounds 3 and 4 , which by a subsequent tetra‐n‐butylammonium bromide (TBAB)‐catalyzed reaction with N H heterocycle compounds (Scheme 1), led to the target compounds 5a – 5j in good yields.