Isolation and structure elucidation of a new compound from the fungus Aspergillus flavipes PJ03-11

A new diphenyl ether 3-methylpentyl-2, 4-dichloroasterrate (2), along with a known diphenyl ether butyl 2, 4-dichloroasterrate (1) were isolated from the metabolites of a wetland fungus Aspergillus flavipes. PJ03-11. The structures of 1 and 2 were determined by extensive NMR and HR–ESI–MS experiments. Compounds 1 and 2 showed weak cytotoxic activity, but both of them showed no antimicrobial activity.     

Synthese von Indolen und Isochinolonen aus Phenylmalonylheterocyclen

A new synthesis of the indole system has been achieved by chclodehydrogenation of amino phenylmalonate heterocycles. Thus, the 4-amino coumarins1 a,b or the 4-amino-2-quinolones1 c–g are converted to the indoles2 with palladium on charcoal in boiling diphenyl ether. The reaction of the aminocompounds1 with diphenyl carbonate yields the fused polycyclic isoquinolones4.

     

Optimized Synthesis of Vinyl Ether Sugars and Vinyl Glycosides through Transfer Vinylation Catalyzed by (4,7‐Ph2‐phen)Pd(OOCCF3)2

Sugar vinyl ethers and vinyl glycosides are conveniently synthesized by catalytic transfer vinylation with butyl vinyl ether, which serves as both the solvent and source of vinyl. The air‐stable catalyst (4,7‐diphenyl‐1,10‐phenanthroline)Pd(OOCCF₃)₂ is prepared in situ from commercially available components.     

Synthesis and Characterization of Polyesterimides Containing Ether Linkages

Abstract

Three novel dicarboxylic acids, bis-4,4′-[N-4(4′-hydroxycarbonyl phenyleneoxy) phthalimido] diphenyl sulfone, bis-4,4′-[N-4(4′-hydroxycarbonyl phenyleneoxy) phthalimido] diphenyl methane, and bis-4,4′-[N-4(4′-hydroxycarbonyl phenyleneoxy) phthalimido] diphenyl ether, were synthesized, and several polyesterimides were prepared from diacid chlorides and bisphenols by solution polycondensation. The polymers were obtained in 65–88% yield and had inherent viscosities in the 0.18 to 0.64 dL/g range. The polymers were characterized by IR, elemental analysis, x-ray, TGA, DSC, and solubility tests. All the polymers were readily soluble in polar aprotic solvents and had a 10% weight loss temperature above 375°C in nitrogen.     

Rational design of InhA inhibitors in the class of diphenyl ether derivatives as potential anti-tubercular agents using molecular dynamics simulations

A series of diphenyl ether derivatives were developed and showed promising potency for inhibiting InhA, an essential enoyl acyl carrier protein reductase involved in mycolic acid biosynthesis, leading to the lysis of Mycobacterium tuberculosis. To understand the structural basis of diphenyl ether derivatives for designing more potent inhibitors, molecular dynamics (MD) simulations were performed. Based on the obtained results, the dynamic behaviour in terms of flexibility, binding free energy, binding energy decomposition, conformation, and the inhibitor–enzyme interaction of diphenyl ether inhibitors were elucidated. Phe149, Tyr158, Met161, Met199, Val203 and NAD+ are the key residues for binding of diphenyl ether inhibitors in the InhA binding pocket. Our results could provide the structural concept to design new diphenyl ether inhibitors with better enzyme inhibitory activity against M. tuberculosis InhA. The present work facilitates the design of new and potentially more effective anti-tuberculosis agents.     

Diphenyl ethers from a marine-derived isolate of Aspergillus sp. CUGB-F046

One new diphenyl ether, diorcinol K (1), along with three known compounds, diorcinols D (2), F (3) and I (4) were isolated from the fermentation media of a marine-derived fungus Aspergillus sp. CUGB-F046 which was isolated from a sediment sample collected from the Bohai Sea, China. Their structures were elucidated by detailed spectroscopic methods. Compounds 1, 2 and 4 displayed significant antibacterial activities against Staphylococcus aureus and methicillin-resistant S. aureus with MIC values of 3.125, 6.25 and 6.25 μg/mL, respectively.     

Phase relationships and thermodynamic interactions in isotactic polypropylene–diluent systems

Phase relationships of isotactic polypropylene in various organic diluents were investigated. The diluents used were aliphatic alcohols, alkyl phenols, aryl phenols, diphenyl derivatives, alkyl aryl ethers, esters, and others. Among the diluents examined, n-butyl alcohol, p-tert-butyl phenol, p-tert-amyl phenol, diphenyl, diphenyl ether, benzyl phenyl ether, dibenzyl ether, and benzyl propionate were found to be theta solvents for isotactic polypropylene at temperatures in the range 120–190°C. For these theta solvents, the thermodynamic interaction parameters were determined. The results are discussed in relation to the type of diluent.     

Capacites calorifiques de durcisseurs amines et resines epoxydes

Heat capacities of some amines (aniline, N-methyl aniline, meta-phenylene diamine, diamino diphenyl methane, diamino diphenyl sulfone and diamino diphenyl oxide) and two epoxy resins (phenyl glycidyl ether and diglycidyl ether of bisphenol A) have been determined in the solid and liquid states versus temperature. The heat capacity increments related to the functional groups have been evaluated compared to references like benzene, aniline and phenyl glycidyl ether.     

Synthese von Benzofuranen durch Cyclodehydrierung von Phenylmalonylheterocyclen

Phenylmalonyl heterocyclic compounds such as the quinolones1a–c or3, benzoquinolizinones6a, b and the phenalenones8a, b can be converted to benzofuranes (2a–c, 7a, b and9a, b) by cyclodehydrogenation with Pd/C in boiling diphenyl ether. 2-Phenylchinchonic acid (10) reacts under the same conditions to the dimeric benzofuroquinoline12: the decarboxylated quinoline11 however gives the monomer13.

Herrn Prof. Dr.G. Zigeuner zur Vollendung seines 60. Lebensjahres gewidmet.     

Phase relationships and thermodynamic interactions in linear polyethylene–diluent systems

Phase equilibria between linear polyethylene and a number of organic diluents of varying type have been investigated. The diluents include aliphatic alcohols, alkyl phenols, aryl phenols, diphenyl derivatives, alkyl aryl ethers, esters, and ketones. It is found that n-octyl alcohol, n-decyl alcohol, n-lauryl alcohol, p-tert-amyl alcohol, p-octyl phenol, p-nonyl, phenol, diphenyl, diphenylmethane, diphenyl ether, benzyl phenyl ether, and anisole are Θ-solvents for linear polyethylene at temperatures between 120 and 200°C. Thermodynamic interactions are discussed in relation to the type of diluent.     

Synthesis of Pyridothienopyridines and Arylazothienopyridines

Treatment of aminothienopyridine 3 with arylidenemalononitrile afford pyridothienopyridine 4. Also condensation of 3 with ethyl ethoxymethylene-cyanoacetae afford compound 5, which was cyclized in diphenyl ether into pyridothienopyridine 6. Thiourea derivative 7 was cyclized using Br₂/AcOH, and ethyl chloroacetate to afford thiazolothienopyridine 8 and thiazolidinylthienopyridine 9 respectively. Compound 15 was condensed with aromatic aldehydes to give the corresponding arylidenethienopyridines 16a–d. The latter compounds were underwent Michael addition with malononitrile to produce pyranothienopyridines 17a–d. Compound 15 was coupled with aromatic diazonium chloride to give the corresponding 2-arylazothienopyridine derivatives 20, but when treated with nitrous acis it dimerised into compound 19.     

Alkylated polypyrazines

The syntheses of four new monomers and two new polyaromatic pyrazines are described. The monomers; bis-p,p′-(octanoyl)diphenyl ether (Ia), bis-p,p′-(hexadecanoyl)diphenyl ether (Ib), bis-p,p′-(α-bromooctanoyl)diphenyl ether (IIa), and bis-p,p′-(α-bromohexadecanoyl)diphenyl ether (IIb), were produced by Friedel-Crafts acylation of diphenyl ether with the corresponding acyl chloride and subsequent α-bromination. Prepolymers were synthesized by the condensation of (IIa) and (IIb) with ammonia in N,N-dimethylformamide (DMF), and polymers were prepared by subsequent melt condensation of the prepolymer to produce poly[2,5-(oxydiphenylene)-3,6-(dihexyl)pyrazine] (IIIa), and poly[2,5-(oxydiphenylene)-3,6-(ditetradecyl)pyrazine] (IIIb). Polymer IIIa was thermally (stable at >400°C while polymer IIIb was a tacky substance). The inherent viscosity of IIIa produced by 12 hr of melt condensation was 0.30 dl/g in formic acid. Additional heating in excess of 24 hr gave a slightly soluble polymer. The inherent viscosity of IIIb produced by 40 hr of melt condensation was 0.37 dl/g in formic acid.     

Unperturbed chain dimensions of isotactic polypropylene in theta solvents

The unperturbed mean-square end-to-end distance 〈R₀²〉 and its temperature variation d In 〈R₀²〉/dT for isotactic polypropylene have been estimated from intrinsic viscosity data in three theta solvents, i.e., diphenyl, diphenyl ether, and dibenzyl ether, measured at their θ temperatures as determined by precipitation temperature measurements. The characteristic ratios, 〈R₀²〉/nl², where n is the number of bonds of length l in the main chain, evaluated by assuming Φ = 2.87 × 10²¹, are 5.80 in diphenyl (at θ = 125.1°C.), 5.41 in diphenyl ether (at θ = 142.8°C.), and 4.56 in dibenzyl ether (at θ = 183.2°C.). These values lead to the temperature coefficient d In 〈R₀²〉/dT = ?4.09 × 10^?3 deg.^?1 Results are compared with the data previously reported on polyethylene.     

γ-Radiation-Initiated Formation of Phenol and Diphenyl Ether from Halobenzenes

The formation of phenol was observed in aqueous alkaline solutions of chlorobenzene. Diphenyl ether was formed in aqueous tert-butanol solutions of chlorobenzene and bromobenzene in the presence of phenoxide ions. An increase in the temperature of irradiation resulted in an increase in the yields of phenol and diphenyl ether. At a temperature higher than 150°C, chain reactions of phenol and diphenyl ether formation occurred. It is likely that the dissociation of halobenzene radical anions is the rate-limiting step of the processes.     

Copoly(Aryl Ether)s Containing 1,10‐Phenanthroline Moieties

Abstract

Poly(aryl ether)s were synthesized by reaction of 4,7‐dichloro‐3,8‐diphenyl‐1,10‐phenanthroline and 4,7‐dichloro‐2,9‐dimethyl‐1,10‐phenanthroline with bisphenol A (BPA) in the presence of potassium carbonate in N,N‐dimethylacetamide or N‐methylpyrrolidinone. High molecular weight homopolymers could not be prepared because of the insolubility of the polymers resulting in premature precipitation from the reaction mixture. Soluble, high molecular weight copolymers were readily prepared containing up to 70 mol% of the 1,10‐phenanthroline moieties. The copolymers were all highly fluorescent with blue emission.     

Collisional activation spectra. Gas phase [C12H10O]+˙ and [C12H9O]+ ions from dephenyl ether,diphenyl carbonate,and o-, m- and p-phenylphenol

[C₁₂H₁₀O]⁺˙ ions in the mass spectra of diphenyl ether and diphenyl carbonate have the same structure, but one which differs from that of these ions from phenylphenol. [C₁₂H₉O]⁺ ions from all three compounds have isomerized to a common structure.     

Synthesis of Some Specifically Deoxygenated D-Hexopyranosyl Phosphates

Abstract

A number of diphenyl α-glucopyranosyl and xylopyranosyl phosphates (4, 7, 11. 15, 19, and 25) were prepared from their respective glycosyl chlorides by reaction with silver diphenyl phosphate. These sugar phosphates are of interest as enzyme substrates in deoxy sugar biosynthesis.     

Synthesis of copolymers of poly(ether sulfone ether ketone ketone) and poly(ether ketone diphenyl ketone ether ketone ketone) by electrophilic Friedel–Crafts solution polycondensation

A new monomer, 4,4′‐bis(4‐phenoxybenzoyl)diphenyl(BPOBDP), was synthesized via a two‐step synthetic procedure. A series of novel poly(ether sulfone ether ketone ketone)/poly(ether ketone diphenyl ketone ether ketone ketone) copolymers were prepared by electrophilic Friedel–Crafts solution copolycondensation of isophthaloyl chloride (IPC) with a mixture of 4,4′‐diphenoxydiphenylsulfone (DPODPS) and 4,4′‐bis(4‐phenoxybenzoyl)diphenyl (BPOBDP), in the presence of anhydrous aluminum chloride and N‐methylpyrrolidone (NMP) in 1,2‐dichloroethane (DCE). The copolymers with 10–50 mol% DPODPS are semicrystalline and have remarkably increased T_gs over commercially available PEEK and PEKK. The copolymers with 40–50 mol% DPODPS had not only high T_gs of 170–172°C, but also moderate T_ms of 326–333°C, which are extremely suitable for melt processing. These copolymers have tensile strengths of 96.5–108.1 MPa, Young's moduli of 1.98–3.05 GPa, and elongations at break of 13–26% and exhibit excellent thermal stability and good resistance to acidity, alkali, and common organic solvents. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis and chemistry of the phenoxasilins and dihydro-dibenzo-oxasilepins

Formation of both sila-functional and carbo-functional phenoxasilins from diphenyl ether and o,o′-dibromodiphenyl ether precursors is described. Tricyclic oxasilepins are formed from o,o′-dibromobenzylphenyl ether by metallation with n-BuLi followed by reaction with dichlorosilanes as well as by ring expansion of an appropriate phenoxasilin. Reactions at the silicon center and at the ring methylene carbon of the oxasilepins are reported, as well as attempts to generate oxasilocins.     

激光诱导的亚硝酸与二苯醚的反应机理

355 nm光照下利用瞬态吸收光谱技术进行了有氧、无氧条件下二苯醚与亚硝酸体系的反应机理研究, 考察了其中瞬态物种的衰减行为, 并对其光解产物进行了GC-MS分析. 研究表明, HNO₂在355 nm紫外光的照射下产生的OH自由基和二苯醚反应生成C₁₂H₁₀O-OH 加合物, N₂条件下C₁₂H₁₀O-OH衰减的速率常数为(1.86±0.14)×10⁵ s^－1, 在有氧条件下, C₁₂H₁₀O-OH可转化为C₁₂H₁₀O-OHO₂, 衰减的速率常数为(6.6±0.4)×10⁶ s^－1. N₂条件下最终产物为苯酚、2-羟基二苯醚、4-羟基二苯醚、4-硝基二苯醚.