Macrocyclic oligomeric arylene ether ketones: Synthesis and polymerization

Some novel macrocylic(arylene ether ketone)oligomers were synthesized in high yields by a nucleophilic aromatic substitution reaction of 4,4'-dinitrobenzophenone with bisphenols in the presence of anhydrous potassium carbonate under pseudo-high-dilution conditions. Detailed structural characterization of these oligomers by matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS), H-1 NMR and FT-IR confirmed their cyclic nature and the compositions of the oligomeric mixtures was indicated by GPC analysis. Ring-opening polymerization of cyclic oligomers 3a to a high molecular weight polymer with M-w of 52.3 and M-n of 17.2 k was achieved by heating at 280 degrees C for 40 min in the presence of a nucleophilic initiator.

Catalysis of hydrotalcite-like compounds in liquid phase oxidation: (II) - Oxidation of p-cresol to p-hydroxybenzaldehyde

Hydrotalcite-like compounds (HTLcs): CoMAlCO3-HTLcs (M=Cu2+, Ni2+, Mn2+, Cr3+, Fe3+), were synthesized by coprecipitation and characterized with XRD and IR. The catalysis of these HTLcs and their calcined products were studied in the p-cresol oxidation, and the effects of the temperature of HTLcs calcination, the ratio of Co/Cu, different promoters, reaction temperatures and reaction times on reaction activities were investigated. It has been found that calcined HTLcs have higher activity than uncalcined samples and mechanical mixed oxides in this reaction. The best yield was obtained from the CoCuAlCO3-HTLc (Co/Cu/Al=3:1:1) calcined at 450 degrees C. A tentative reaction mechanism was also proposed. (C) 1998 Elsevier Science B.V.

Catalysis of hydrotalcite-like compounds in liquid phase oxidation: (I) phenol hydroxylation

Hydrotalcite-like compounds (HTLcs): (CuMAlCO3)-Al-II-HTLcs, where M-II=Co2+, Ni2+, Cu2+, Zn2+ and Fe2+, were synthesized by coprecipitation and characterized with XRD and IR. The catalysis of these HTLcs was studied in the phenol hydroxylation by H2O2 in liquid phase; then the effects of the ratio of Cu/Al, reaction temperature, solvent and pH of medium were investigated. It has been found that the uncalcined HTLcs have higher activities than those of calcined samples in this reaction. The catalyst CuAlCO3-HTLcs having Cu/Al=3 efficiently oxidized phenol and gave high yields of the corresponding diphenols in appropriate reaction conditions. A tentative reaction mechanism is also proposed. (C) 1998 Elsevier Science B.V.

A study of catalysis of copper-aluminium hydrotalcite-like compounds in the phenol hydroxylation

Copper-Aluminium Hydrotalcite-like compounds are synthesized by coprecipitation and characterized with XRD and IR. Catalysis of the above mentioned HTLcs are investigated in the phenol hydroxylation, good results are obtained. Meanwhile, the effects of the ratio of Cu/Al, reaction temperature, reaction medium and pH of reaction system are discussed, The reaction mechanism is also proposed.

The oxidative demethylation of 24-membered hexa-aza macrocyclic bicopper(I) complex - The mimicking for monooxygenase

By [2 + 2] Schiff base condensation of 5 - bromo - 2 - methoxylbenzene - 1,3 - dicarboxaldehyde with diethylenetriamine, a new hexaaza 24 - membered macrocyclic ligand was obtained,which formed a macrocyclic binuclear copper(I) complex in the presence of [Cu . (CH3CN)(4)]ClO4. When the copper(I) complex was oxidized in air or oxygen, a new macrocyclic binuclear copper( II) complex was obtained. The copper( II.) complex was characterized by several methods and its oxidized products was characterized by H-1 NMR. The results show that during oxidation, a methoxyl group in the ligand ring broke; and the phenoxy - and water - bridged Cu(II) complex formed. In oxidation of monooxygenase such as ligninase, oxidative demethylation also happened. Therefore this work mimicked this process for the first time by using macrocyclic complex. The quantity of absorbed oxygen and the absorption rate of oxygen were determined.

Structure, luminescence and magnetic properties of AgLnW(2)O(8) (Ln = Eu, Gd, Tb and Dy) compounds

Four new compounds AgLnW(2)O(8) (Ln = Eu, Gd, Tb and Dy) are prepared by solid-state reactions. They crystallize with a scheelite-related monoclinic symmetry. Infrared (IR) spectra show complicated absorption transitions in the region of 1000-400 cm(-1) that are similar to those of AgLnMo(2)O(8). Broad excitation and emission bands of the tungstate group are observed in AgGdW2O8 and AgTbW2O8 with a large Stokes shift, 12 573 and 12 387 cm(-1), respectively. Excitation and emission spectra of AgLnW(2)O(8) (Ln = Eu, Gd and Tb) show that energy transfer from the tungstate to EU3+, Gd3+ and Tb3+ occurs and that Eu3+ ions occupy a single crystallographic site with the C-2 Site symmetry. (C) 1997 Elsevier Science Ltd. All rights reserved.

Polymerization of ethylene by zirconocene-B(C6F5)(3) catalysts with aluminum compounds

Ethylene polymerization by zirconocene-B(C6F5)(3) catalysts with various aluminum compounds has been investigated. It is found that the catalytic activity depended on zirconocenes used, and especially on the type of aluminum compounds. For Et(H(4)Ind)(2)ZrCl2 (H(4)Ind : tetrahydroindenyl), the activity decreases in the following order: Me3Al > i-Bu3Al > Et3Al much greater than Et2AlCl. While for Cp2ZrCl2(Cp : cyclopentadienyl), it varies as follows: i-Bu3Al > Me3Al much greater than Et3Al. Furthermore, the activity is significantly affected by the addition mode of the catalytic components, which may imply that the formation of active centers is associated with an existing concentration of catalytic components. Results of thermal behavior of polyethylene (PE) studied by differential scanning calorimetry(DSC) show that crystallinity of the polymer prepared with Et3Al is higher than that with Me3Al or i-Bu3Al. It is also found that the number-average molecular weight ((M) over bar) of the polymers prepared with Me3Al or i-Bu3Al is much higher than that with Et3Al. H-1-NMR studies substantiate that i-Bu3Al is a more efficient alkylation agent of Cp2ZrCl2 in comparison with Me3Al. (C) 1997 John Wiley & Sons, Inc.

Catalysis of copper-containing transition metal hydrotalcite-like compounds in the phenol hydroxylation with hydrogen peroxide

Hydrotalcite-like compounds containing carbonate ion as the interlayer anion were prepared by coprecipitation under low supersaturation condition by mixing an aqueous solution of metal nitrates with an aqueous solutions of NaOH and Na2CO3, at room temperature, maintaining pH = 8-10 with vigorous stirring, Following the mixing, the resulting heavy slurry was aged at 353 K for 18 h with vigorous stirring, The precipitate was then filtered, washed several times with hot distilled water and dried in air at 353 K overnight, In this way, CuMI AlCO3-HTLcs and M-I AlCO3-HTLcs were synthesized and characterized by means of XRD and IR, The catalysis of the above mentioned HTLcs were investigated in the phenol hydroxylation with H2O2. The results indicated that all of the copper-containing HTLcs had a higher catalytic activity in the reaction, However, those catalysts that did not contain copper had no catalytic activity in this reaction, This means that copper was the active center in the phenol hydroxylation. Meanwhile, the mechanism was also proposed, which could be used to explain the main reason for higher activity for CuCuAlCO3-HTLcs in the phenol hydroxylation and the effect of Mg2+, Zn2+, Co2+, Ni2+ on activity of CuMI AlCO3-HTLcs.

Synthesis, structure and ring-opening polymerization of macrocyclic arylates containing phthalic unit

A series of macrocyclic arylate dimers have been selectively synthesized by an interfacial polycondensation of o-phthaloyldichloride with bisphenols. A combination of GPC, FAB-MS, H-1 and C-13 NMR unambiguously confirmed the cyclic nature. Although single-crystal X-ray analysis of two such macrocycles reveals no severe strain on the cyclic structures, these macrocycles can undergo facile melt polymerization to give high molecular weight polyarylates.

Fragmentations of some bifunctional phenylether compounds by intermediate ion/neutral complexes

The fragmentations of three bifunctional phenylether compounds including 2-(2, 6-dichloro)phenoxyl propionitrile, N-hydroxyl-4-butoxyl phenylacetyl amine(bufexamc) and 2-(1-methylethoxyl) phenol methylcarbamate (Propoxur) under electron impact ionization were reported, Metastable ion(MI) and collision-induced dissociation(CID) at a low energy have been used to study the fragmentation pathways from molecular ions. Apart from the simple bond cleavages, and the unimolecular dissociations via ion/neutral complex intermediate as a competitive mechanism were demonstrated, Moreover, the intramolecular hydrogen transfer and double hydrogen transfers in the fragmentations of these compounds were discussed in detail.

Isolation, spectra, structure, and ring-opening polymerization of strained macrocyclic aryl(ether ketone) dimer

Macrocyclic arylene ether ketone dimer was isolated from a mixture of cyclic oligomers obtained by the nucleophilic substitution reaction of bisphenol A and 4,4'-difluorobenzophenone and easily polymerized to high molecular weight linear poly(ether ketone). The cyclic compound was characterized by FTIR, H-1- and C-13-NMR, and single-crystal x-ray diffraction. Analysis of the spectral and crystal structure reveals extreme distortions of he phenyl rings attached to the isopropylidene center and of the turning points of the molecular polygons. The release of the ring strain on ring-opening combined with entropical difference between the linear polymer chain and the more rigid macrocycle at temperatures of polymerization may be the proposed motivating factors in the polymerization of this precursor to high molecular weight poly(ether ketone). (C) 1997 John Wiley & Sons, Inc.

Crystal structure of a Pr-III complex with a novel macrocyclic ligand

The crystal structure of a novel macrocyclic ligand complex of Pr-III, C112H178O52N8S4Pr2, [Pr2L2(HL)(2)(H2O)(6)]. 22H(2)O is reported. The macrocyclic ligand has pendant acetic acid through which the ligand is coordinated to the Pr-III ion. For the dimeric unit, [Pr2L2(HL)(2)(H2O)(6)], two Pr-III ions are connected by two bridging-chelating carboxyl groups and two bridging carboxyl groups of the ligands, and each Pr-III ion is also bonded to a unidentate carboxyl group of the ligand and three water molecules. The dimeric units are bridged by four ligands through their carboxyl groups to form an infinite one-dimensional chain. The coordination number of the Pr-III ion is nine, with a distorted tricapped trigonal prismatic configuration. (C) 1997 Elsevier Science Ltd.

Synthesis, structure, and ring-opening polymerization of macrocyclic aromatic esters: A new route to high-performance polyarylates

A series of macrocyclic arylate dimers have been efficiently synthesized by an interfacial polycondensation of o-phthaloyl dichloride with bisphenols. A combination of GPC, FAB MS, and H-1 and C-13 NMR unambiguously confirmed the cyclic nature. Although single-crystal X-ray analysis of one such macrocycle reveals no severe strain on the cyclic structure, these macrocycles can undergo facile melt polymerization to give high molecular weight polyarylates.

Structure and luminescence properties of some new AgLnW(2)O(8) compounds

Three new compounds, AgLnW(2)O(8) (Ln(3+)=Eu, Gd or Tb), have been prepared by a solid-state reaction and crystallize with a scheelite-related monoclinic symmetry. Their IR spectra show absorption transitions in the region 1000-400 cm(-1) similar to KLnW(2)O(8). Broad excitation and emission bands of the tungstate group with a large Stokes shift (12573 cm(-1)) are observed in AgGdW2O8. Excitation and emission spectra of AgLnW(2)O(8) (Ln=Eu or Tb) show that energy transfer from tungstate to Eu and Tb occurs and that Eu3+ ions occupy a unique crystallographic site with C-2 site symmetry.