Xanthylium salts formation involved in wine colour changes

Summary The reaction of (+)-catechin in wine-like model solution was investigated. First appearance of colourless dimeric compounds consisting of two flavanol units linked by carboxy-methine bridge was observed. Their isolation and further incubation was found to yield two types of yellowish pigments showing visible absorption maxima at 440 and 460 nm, respectively. Mass spectroscopy (MS) spectral analysis showed that the first type were xanthylium salt pigments formed by dehydration of the colourless compounds followed by an oxidation process. The loss of a water molecule was shown to take place between two A ring hydroxyl groups of the colourless dimers. The second type were shown to be ester derivatives of the first ones. Thus ethylester of xanthylium salt was obtained and fully characterized by mass and nuclear magnetic resonance (NMR) spectroscopy. Esterification was found to involve the colourless compound before dehydration and thus a general scheme for xanthylium salt formation was postulated. The proposed scheme constitutes a new xanthylium formation pathway as up to now only anthocyanin-flavanol reactions were supposed to form xanthylium salt derivatives during wine ageing. This work also provides new support to the contribution of xanthylium salt in colour evolution observed during wine ageing which is generally expressed in an increase of absorption in the 400–500 nm, region of xanthylium salt absorption maxima.     

Nano-CuFe2O4@SO3H Catalyzed Efficient One-Pot Cyclo-Dehydration of Dimedone and Synthesis of Chromeno[4,3-b]chromenes

Chlorosulfonic acid immobilized on CuFe₂O₄ nanoparticles (nano-CuFe₂O₄@SO₃H) was evaluated as a recoverable catalyst for the one-pot cyclo-dehydration of dimedone and synthesis of chromeno[4,3-b]chromene derivatives by reaction of arylaldehydes, dimedone or 1,3-cyclohexanedione, with 3-hydroxycoumarine or 4-hydroxycoumarine in good to excellent yield. Also, 2,2′-Arylmethylene bis(3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) was synthesized by the reaction of aromatic aldehyde and dimedone using nano-CuFe₂O₄ in ethanol at room temperature. The catalyst could be recycled several times without significant loss of its catalytic activity. Clean methodologies, easy work-up procedure, high yield and simple preparation of the catalyst are some advantages of this procedure.     

Phenoxaphosphino‐Modified Xantphos‐Type Ligands in the Rhodium‐Catalysed Hydroformylation of Internal and Terminal Alkenes

The solubility of the modifying ligand is an important parameter for the efficiency of a rhodium‐catalysed hydroformylation system. A facile synthetic procedure for the preparation of well‐defined xanthene‐type ligands was developed in order to study the influence of alkyl substituents at the 2‐, and 7‐positions of the 9,9‐dimethylxanthene backbone and at the 2‐, and 8‐positions of the phenoxaphosphino moiety of ligands 1 – 16 on solubility in toluene and the influence of these substituents on the performance of the ligands in the rhodium‐catalysed hydroformylation. An increase in solubility from 2.3 mmol⋅L⁻¹ to >495 mmol⋅L⁻¹ was observed from the least soluble to the most soluble ligand. A solubility of at least 58 mmol⋅L⁻¹ was estimated to be sufficient for a large‐scale application of these ligands in hydroformylation. Highly active and selective catalysts for the rhodium‐catalysed hydroformylation of 1‐octene and trans‐2‐octene to nonanal, and for the hydroformylation of 2‐pentene to hexanal were obtained by employing these ligands. Average rates of >1600 (mol aldehyde) × (mol Rh)⁻¹×h⁻¹ {conditions: p(CO/H₂) = 20 bar, T = 353 K, [Rh] = 1 mM, [alkene] = 637 mM} and excellent regio‐selectivities of up to 99% toward the linear product were obtained when 1‐octene was used as substrate. For internal olefins average rates of >145 (mol aldehyde)×(mol Rh)⁻¹×h⁻¹ {p(CO/H₂) = 3.6–10 bar, T = 393 K, [Rh] = 1 mM, [alkene] = 640–928 mM} and high regio‐selectivities up to 91% toward the linear product were obtained.     

Synthesis and properties of novel polyamides containing sulfone‐ether linkages and xanthene cardo groups

In order to obtain polyamides with enhanced solubility and processability, as well as good mechanical and thermal properties, several novel polyamides containing sulfone‐ether linkages and xanthene cardo groups based on a new diamine monomer, 9,9‐bis[4‐(4‐aminophenoxy)phenyl]xanthene (BAPX), were investigated. The BAPX monomer was synthesized via a two‐step process consisting of an aromatic nucleophilic substitution reaction of readily available 4‐chloronitrobenzene with 9,9‐bis(4‐hydroxyphenyl)xanthene in the presence of potassium carbonate in N,N‐dimethylformamide, followed by catalytic reduction with hydrazine and Pd/C. Four novel aromatic polyamides containing sulfone‐ether linkages and xanthene cardo groups with inherent viscosities between 0.98 and 1.22 dL g^?1 were prepared by low‐temperature polycondensation of BAPX with 4,4′‐sulfonyldibenzoyl chloride, 4,4′‐[sulfonyl‐bis(4‐phenyleneoxy)]dibenzoyl chloride, 3,3′‐[sulfonyl‐bis(4‐phenyleneoxy)]dibenzoyl chloride and 4,4′‐[sulfonyl‐bis(2,6‐dimethyl‐1,4‐phenyleneoxy)]dibenzoyl chloride in N,N‐dimethylacetamide (DMAc) solution containing pyridine. All these new polyamides were amorphous and readily soluble in various polar solvents such as DMAc and N‐methylpyrrolidone. These polymers showed relatively high glass transition temperatures in the range 238–298 °C, almost no weight loss up to 450 °C in air or nitrogen atmosphere, decomposition temperatures at 10% weight loss ranging from 472 to 523 °C and 465 to 512 °C in nitrogen and air, respectively, and char yields at 800 °C in nitrogen higher than 50 wt%. Transparent, flexible and tough films of these polymers cast from DMAc solution exhibited tensile strengths ranging from 78 to 87 MPa, elongations at break from 9 to 13% and initial moduli from 1.7 to 2.2 GPa. Primary characterization of these novel polyamides shows that they might serve as new candidates for processable high‐performance polymeric materials. Copyright © 2010 Society of Chemical Industry     

Screening Xanthene Dyes for Visible Light‐Driven Nicotinamide Adenine Dinucleotide Regeneration and Photoenzymatic Synthesis

Regeneration of the nicotinamide cofactor is a critical issue in biocatalysis. Herein we have screened xanthene dyes for a highly efficient, visible light‐driven photochemical regeneration of cofactors and enzymatic synthesis. Superior catalytic performance was observed with several xanthene dyes such as phloxine B, erythrosine B, eosin Y, and rose bengal. We found that the photo‐ and electrochemical properties of the xanthene dyes were affected by the halogen atom substitution, which is a key factor in the efficient light‐induced electron transfer from the donor molecule to the catalytic mediator.     

Synthesis and characterization of new cardo poly(ether imide)s derived from 9,9‐bis [4‐(4‐aminophenoxy)phenyl]xanthene

A series of new cardo poly(ether imide)s bearing flexible ether and bulky xanthene pendant groups was prepared from 9,9‐bis[4‐(4‐aminophenoxy)phenyl]xanthene with six commercially available aromatic tetracarboxylic dianhydrides in N,N‐dimethylacetamide (DMAc) via the poly(amic acid) precursors and subsequent thermal or chemical imidization. The intermediate poly(amic acid)s had inherent viscosities between 0.83 and 1.28 dL/g, could be cast from DMAc solutions and thermally converted into transparent, flexible, and tough poly(ether imide) films which were further characterized by X‐ray and mechanical analysis. All of the poly(ether imide)s were amorphous and their films exhibited tensile strengths of 89–108 MPa, elongations at break of 7–9%, and initial moduli of 2.12–2.65 GPa. Three poly(ether imide)s derived from 4,4′‐oxydiphthalic anhydride, 4,4′‐sulfonyldiphthalic anhydride, and 2,2‐bis(3,4‐dicarboxyphenyl))hexafluoropropane anhydride, respectively, exhibited excellent solubility in various solvents such as DMAc, N,N‐dimethylformamide, N‐methyl‐2‐pyrrolidinone, pyridine, and even in tetrahydrofuran at room temperature. The resulting poly(ether imide)s with glass transition temperatures between 286 and 335°C had initial decomposition temperatures above 500°C, 10% weight loss temperatures ranging from 551 to 575°C in nitrogen and 547 to 570°C in air, and char yields of 53–64% at 800°C in nitrogen. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fe3O4@SiO2-SnCl4: An Efficient Catalyst for the Synthesis of Xanthene Derivatives under Ultrasonic Irradiation

Grafting of SnCl₄ on the Fe₃O₄@SiO₂ nanoparticles afforded Fe₃O₄@SiO₂-SnCl₄ as a novel inorganic heterogenous catalyst, which was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), vibrating sample magnetometry (VSM), Field Emission Scanning Electron Microscopy (FE-SEM), and transmission electron microscopy (TEM). In this research, we report a convenient and efficient direct protocol for the preparation of xanthene derivatives via condensation of β-naphthol, dimedone, or mixture of β-naphthol and dimedone with various aromatic aldehydes in the presence of the catalytic amount of Fe₃O₄@SiO₂-SnCl₄ under ultrasonic irradiation. This procedure has a lot of advantages such as: very easy reaction conditions, absence of any tedious workup, or purification, and much milder method. The corresponding products have been obtained in excellent yields, high purity, and short reaction times.     

一种基于氧杂蒽结构的“Turn-Off”型荧光探针研究及对磷酸酯类物质检测

设计了一种基于氧杂蒽结构的"Turn-Off"型荧光探针(P3),在生理pH条件下对磷酸根(Pi)较好的荧光淬灭性能,在与其它竞争性含氧阴离子(硫酸根、硝酸根、碳酸氢根)以及其它常见阴离子(氟离子、氯离子、溴离子等)对该识别的竞争性影响考察中,亦显示了较好的特异性。从荧光滴定法得到荧光探针(P3)与磷酸根(Pi)形成超分子复合物的摩尔比为1∶1,复合物稳定常数K为5.28*103。通过量子化学计算表明磷酸根与!共轭体系产生了较强的相互作用,并导致P3分子平面上翘,在一定程度上破坏了原先的共面型,磷酸根上氧部位的孤对电子与!共轭体系存在着轨道交叠,即p-!共轭作用。可将此探针应用于磷酸酯类物质的检测。     

Fluorescence Efficiency of Laser Dyes

The fluorescence efficiency of xanthene dyes, oxazine dyes, and 7-aminocoumarins is discussed. Relations with the molecular structure are pointed out and dependence on solvent and temperature is explained. Several new fluorescence standards are suggested.     

Synthesis and properties of novel aromatic polyamides with xanthene cardo groups

Two novel monomers, 9,9‐bis[4‐(4‐carboxyphenoxy)phenyl]xanthene (BCAPX) and 9,9‐bis[4‐(4‐aminophenoxy)phenyl]xanthene (BAPX) were prepared in two main steps starting from nucleophilic substitution of 9,9‐bis(4‐hydroxyphenyl)xanthene (BHPX) with p‐fluorobenzonitrile and p‐chloronitrobenzene, respectively. Using triphenyl phosphite and pyridine as condensing agents, two series of polyamides containing xanthene cardo groups with the inherent viscosities (0.82–1.32 dL/g) were prepared by polycondensation from BCAPX with various aromatic diamines or from BAPX with various aromatic dicarboxylic acids in an N‐methyl‐2‐pyrrolidone (NMP) solution containing dissolved calcium chloride, respectively. All new polyamides were amorphous and readily soluble in various polar solvents such as N,N‐dimethylformamide (DMF), NMP, N,N‐dimethylacetamide (DMAc) and pyridine. These polymers showed relatively high glass transition temperatures between 264 and 308°C, decomposition temperatures at 10% weight loss ranging from 502 to 540°C and 488 to 515°C in nitrogen and air, respectively, and char yields at 800°C in nitrogen higher than 56%. Transparent, flexible, and tough films of these polymers cast from DMAc solutions exhibited tensile strengths ranging from 86 to 109 MPa, elongations at break from 13 to 22%, and initial moduli from 2.15 to 2.63 GPa. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010