Abstract: PROBLEM TO BE SOLVED: To provide a nonaqueous electrolyte secondary battery that exhibits excellent charge/discharge efficiency and storage characteristic even at high temperatures SOLUTION: The nonaqueous electrolyte secondary battery has at least a negative electrode including different element materials capable of storing and releasing lithium, a positive electrode including a metal oxide material capable of storing and releasing lithium, and an electrolyte in which a lithium salt is dissolved in an nonaqeuous solvent, wherein the nonaqueous solvent contains, in the electrolyte, 001 to 10 wt% of a compound of general formula (1) as shown below (In the formula, n is an integer equal to or more than three; R 1 and R 2 are each an alkyl in which a part or all of the hydrogen atoms thereof are substituted by fluorine atoms; and R 3 are each independently a hydrogen atom, an alkyl group, an ether group, a carboxylic acid ester group, a carbonic acid ester group or a halogen atom) COPYRIGHT: (C)2004,JPO

Abstract: This paper provides an overview of the recent advances on polymeric photoinitiators for UV curing. During the last decade, significant developments have been achieved in the synthesis of macrophotoinitiators, due to the advantages derived of their macromolecular nature, in comparison with their corresponding low molecular weight analogues. In particular, a variety of macromolecules containing the two main types of free radical photoinitiators: hydrogen-abstracting (thioxanthone, benzil, anthraquinone, camphorquinone) and photofragmenting chromophores (benzoin ether, acylphosphine oxides) are described. For hydrogen-abstracting photoinitiator, the photoinitiation activity have been examined in terms of volume and nature of substituent in the polymeric coil, and their influence to prevent the recombination of radicals favouring their reaction with the monomer. Also, copolymers bearing chromophore and amine groups with potential synergistic effects of activity are reported. It has been found that the approach of the tertiary amine to the chromophore to produce the corresponding exciplexes is dependent on both the monomeric or polymeric nature of chromophore and the tertiary amine. Type II polymeric photoinitiators, such as benzoin ether derivatives having the benzoin methyl ether moieties connected to the main chain through the benzyl aromatic are reported. And a fragmentation mechanism involving the formation of an stable quinoid structure and aliphatic acyl radical is proposed for the above copolymers, which would justified their lower initiating efficiency than the corresponding low molecular weight model. In addition, polymers bearing phosphine oxide moieties are described. The efficiency in the polymerisation of all photoinitiators was found to be similar and irrespective of the presence of flexible spacer in their structure. However, it was found that the flexible oligomethylene spacer enhanced the compatibility of the new polymeric photoinitiators in acrylic adhesive formulations. Finally, polysilanes as photoinitiators are reported. Under UV irradiation, polysilanes undergo main-chain scission leading to free silyl radicals capable of reacting with olefinic monomers. The silyl radicals generated by photolysis can be oxidised by appropriate onium salts to yield cationic initiating species (photoinitiated radical promoted cationic polymerisation). The photoinitiation efficiency of polysilanes having different aliphatic and aromatic side groups has been investigated and compared with commercial low molecular weight photoinitiators as benzoin.

Abstract: Human adipose samples collected in Tokyo, Japan in 1970 and 2000 were analyzed for the presence of polybrominated dibenzo-p-dioxins (PBDDs), dibenzofurans (PBDFs), and diphenyl ethers (PBDEs), and the concentrations in the two groups were compared. As far as we know, the concentrations of the PBDD/Fs in adipose tissue from the general Japanese population are reported for the first time. Three PBDD/F congeners were found in the following adipose tissues: 2,3,7,8-TeBDD, 2,3,7,8-TeBDF, and 2,3,4,7,8-PeBDF. The median concentrations (ranges) of three PBDD/Fs in 1970 and 2000 were 5.1 (3.4−8.3) and 3.4 (1.9−5.3) pg/g lipid wt (l.w.), respectively. For PBDEs, seven PBDE congeners were determined in the following samples: 2,4,4‘-tribromodiphenyl ether (BDE-28), 2,2‘,4,4‘-tetrabromodiphenyl ether (BDE-47), 2,2‘,4,4‘,5-pentabromodiphenyl ether (BDE-99), 2,2‘,4,4‘,6-pentabromodiphenyl ether (BDE-100), 2,2‘,4,4‘,5,5‘-hexabromodiphenyl ether (BDE-153), 2,2‘,4,4‘,5‘,6-hexabromodiphenyl ether (BDE-154), and 2,2‘,3,4,...

Abstract: Catalytic asymmetric aldol reactions in aqueous media have been developed using Pr(OTf)(3) and chiral bis-pyridino-18-crown-6 1. In the asymmetric aldol reaction using rare earth metal triflates (RE(OTf)(3)) and 1, slight changes in the ionic diameters of the metal cations greatly affected the diastereo- and enantioselectivities of the products. The substituents (MeO, Br) at the 4-position of the pyridine rings of the crown ether did not significantly affect the selectivities in the asymmetric aldol reaction, although they affected the binding ability of the crown ether with RE cations and the catalytic activity of Pr(OTf)(3)-crown ether complexes. From X-ray structures of RE(NO(3))(3)-crown ether complexes, it was found that they had similar structures regardless of the RE cations and the crown ethers used. Accordingly, the binding ability of the crown ether with the RE cation and the catalytic activity of the complex are important for attaining high selectivity in the asymmetric aldol reaction. Various aromatic and alpha,beta-unsaturated aldehydes and silyl enol ethers derived from ketones and a thioester can be employed in the catalytic asymmetric aldol reactions using Pr(OTf)(3) and 1, to provide the aldol adducts in good to high yields and stereoselectivities. In the case using the silyl enol ether derived from the thioester, 2,6-di-tert-butylpyridine significantly improved the yields of the aldol adducts.

Abstract: Two methods are used for the isolation of residual lignin: acidolytic and enzymatic hydrolysis. Recently a two-step procedure that is a combination of enzymatic and acidic hydrolyses was proposed. In this paper, the structures of residual lignins isolated by these three methods are compared. Enzymatic hydrolysis gave lignin with the highest yield (83%); however, it contained high amounts of carbohydrates and protein. The molar mass of enzymatic lignin was the highest, indicating that no cleavage of lignin occurred. Acidolysis gave a significantly lower lignin yield (40%), but this lignin was practically free from impurities. The β-aryl ether and lignin-carbohydrate linkages cleaved during the isolation, which was manifested in the decreased molar mass of the lignin as well as in increased phenolic hydroxyl group content. The new two-step isolation procedure gave properties between the preparations of enzymatic and acidolytic hydrolyses. The lignin yield was high (78%), but it contained some impurities, although less than the enzymatic lignin. The lignin-carbohydrate linkages cleaved to some extent, but the β-aryl ether linkages remained intact.

Abstract: Imidazopyridine compounds that contain an ether or thioether functionality at the 1-position are useful as immune response modifiers. The compounds and compositions of the invention can induce the biosynthesis of various cytokines and are useful in the treatment of a variety of conditions including viral diseases and neoplastic diseases. Methods of preparing the compounds and intermediates useful in the preparation of the compounds are also disclosed.

Abstract: A new class of alkyl-chain-appended pyrene derivatives 4–14 were synthesized and evaluated for their gelation abilities. Depending on the nature of the linking group, these compounds gelated a number of organic solvents, either in the presence or in the absence of the acceptor molecule 2,4,7-trinitrofluorenone (TNF). Compounds with ester, ether, or alkyl linkages gelated a number of hydroxylic and hydrocarbon solvents by means of a charge-transfer interaction with TNF, while compounds with amide, urethane and urea linkers formed gels on their own in a variety of solvents by means of π–π stacking and hydrogen-bonding interactions. The Xray crystal structure of urethane (S)-12 showed hydrogen-bonding and stacking features, as suggested by the model. The gels obtained were investigated by spectroscopic and electron microscopic techniques which provided structural insights.

Abstract: A highly regioselective vinylogous aldol reaction catalyzed by SiCl4 and a chiral phosphoramide (R,R)-5, providing delta-hydroxy enones for a variety of aldehyde and dienol ether structures, has been developed. Low catalyst loadings (1 mol %) can be employed, giving the products in good yields, excellent enantioselectivities, and in some cases excellent anti diastereoselectivities. Both simple ester-derived dienol ethers as well as dioxanone-derived dienol ethers are employed. The observed regioselectivity is rationalized in terms of the sensitivity of the catalyst to the steric demands of the nucleophile.

Abstract: The reaction of aryl iodides and bromides with acrolein diethyl acetal in the presence of Pd(OAc)2, nBu4NOAc, K2CO3, KCl, and DMF, at 90 °C until the disappearance of the acetal followed by the addition of 2 N HCl to the crude reaction mixture, affords cinnamaldehydes in good to high yields. A variety of functional groups are tolerated in the aryl halides, including ether, aldehyde, ketone, ester, dialkylamino, nitrile, and nitro groups. The presence of substituents close to the oxidative addition site does not hamper the reaction.

Abstract: As a novel class of proton exchange membrane materials for use in fuel cells, sulfonated poly(phthalazinone ether ketone)s (SPPEKs) were prepared by the modification of poly(phthalazinone ether ketone). Sulfonation reactions were conducted at room temperature with mixtures of 95–98% concentrated sulfuric acid and 27–33% fuming sulfuric acid with different acid ratios, and SPPEK was obtained with a degree of sulfonation (DS) in the desired range of 0.6–1.2. The presence of sulfonic acid groups in SPPEK was confirmed by Fourier transform infrared analysis, and the DS and structures were characterized by NMR. The introduction of sulfonic groups into the polymer chains increased the glass-transition temperature above the decomposition temperature and also led to an overall decrease in the decomposition temperature. Membrane films were cast from SPPEK solutions in N,N-dimethylacetamide. Water uptakes and swelling ratios of SPPEK membrane films increased with DS, and SPPEKs with DS > 1.23 were water-soluble at 80 °C. Proton conductivity increased with DS and temperature up to 95 °C, reaching 10−2S/cm. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 497–507, 2003

Abstract: The convergent total synthesis of gambierol (1) is described. The octacyclic ether framework of 1 was constructed via the intramolecular allylation of α-chloroacetoxy ether followed by ring-closing metathesis. A modified Stille coupling was successfully applied to the synthesis of the triene side chain.

Abstract: The invention relates to a complex of ruthenium of the structural formula I, where X1 and X2 are identical or different and are each an anionic ligand, R1 and R2 are identical or different and can also contain a ring, and R1 and R2 are each hydrogen or/and a hydrocarbon group, the ligand L1 is an N-heterocyclic carbene and the ligand L2 is an uncharged electron donor, in particular an N-heterocyclic carbene or an amine, imine, phosphine, phosphate, stibine, arsine, carbonyl compound, carboxyl compound, nitrile, alcohol, ether, thiol or thioether, where R1, R2, R3 and R4 are hydrogen or/and hydrocarbon groups. The invention further relates to a process for preparing acyclic olefins having two or more carbon atoms or/and cyclic olefins having four or more carbon atoms from acyclic olefins having two or more carbon atoms or/and from cyclic olefins having four or more carbon atoms by an olefin metathesis reaction in the presence of at least one catalyst, wherein a complex is used as catalyst and R′1, R′2, R′3 and R′4 are hydrogen or/and hydrocarbon groups.

Abstract: Nano-reinforced fibres were spun from a semicrystalline high-performance poly(ether ether ketone) containing up to 10 wt% vapour-grown carbon nanofibres using conventional polymer processing equipment. Mechanical tensile testing revealed increases in nanocomposite stiffness, yield stress, and fracture strength for both as-spun and heat-treated fibres. X-ray and differential scanning calorimetry analyses were performed in order to investigate both the orientation of nanofibres within the polymer matrix and the matrix morphology. The carbon nanofibres were found to be well aligned with the direction of flow during processing. Significantly, the degree of crystallinity of the poly(ether ether ketone) matrix was found to increase with the initial addition of nanofibres although the crystal structure was not affected. The measured increase in composite tensile modulus is compared to injection-moulded nanocomposite samples made from the same blends. The results highlight the need to characterise the matrix morphology when evaluating nanocomposite performance and hence deducing the intrinsic properties of the nanoscale reinforcement.

Abstract: The impact of various Lewis bases on the miscibility of siloxane polymers in CO2 was investigated using both ab initio calculations and experimental phase behavior studies. A series of side-chain functional silicones were synthesized containing various Lewis bases in the side chain, and their phase behavior was compared in CO2 at 295 K. Calculations showed that interactions between CO2 and ethers (either a dialkyl ether or the ether oxygen in an ester group) should be as favorable as interactions between CO2 and a carbonyl oxygen. Indeed, phase behavior results seemed to support this, as ether-functional silicones exhibited miscibility pressures as low or lower than acetate-functional analogues. Further, a keto-functional material was not nearly as CO2-philic as the acetate functional analogue. In general, the location of the phase boundary in CO2 is governed by a balance between forces working to increase miscibility pressures, such as increased cohesive energy density of the polymer or factors suppressi...

Abstract: Direct addition of anthocyanins and flavan-3-ols was investigated in a model system by incubating malvidin 3-glucoside and (-)-epicatechin in ethanol. Analysis of reaction products by high-performance liquid chromatography coupled to electrospray ionization mass spectrometry (HPLC/ESI-MS) before and after thiolysis showed the formation of colorless dimers detected at m/z 781 in the negative ion mode, with retention times and spectroscopic characteristics identical to those of compounds detected in wine, which contain one malvidin 3-glucoside unit and one flavanol unit. On the basis of their resistance to thiolysis, these compounds were postulated to be bicyclic dimers linked with both carbon-carbon and ether bonds as observed in the case of A type proanthocyanidins. The major dimer analyzed by NMR experiments was identified as malvidin 3-glucoside(C2-O-C7,C4-C8)epicatechin, confirming this hypothesis. A similar assay was performed with (+)-catechin instead of (-)-epicatechin, and the formation of bicyclic dimers was also observed.

Abstract: The synthesis of a new bis(ether carboxylic acid), 2,2-bis(4-carboxyphe- noxy)-9,9-spirobifluorene, in which two orthogonally arranged carboxyphenoxyflu- orene entities are connected through an sp 3 carbon atom (the spiro center), is reported. The direct phosphorylation polycondensation of this diacid monomer with various aromatic diamines yields aromatic polyamides containing 9,9-spirobifluorene moieties in the main chain. The presence of the spiro segment restricts the close packing of the polymer chains and decreases interchain interactions, resulting in amorphous poly- amides with enhanced solubility, and high glass-transition temperatures and good thermal stability are maintained through controlled segmental mobility. The glass- transition temperatures of these polyamides are in the range of 234 -306 °C, with 10% weight losses occurring at temperatures above 530 °C. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1160 -1166, 2003

Abstract: Disclosed herein are compounds of formula (I), wherein R1 is hydroxy or NHSO2R1A wherein R1A is (C1-8)alkyl, (C3-7)cycloalkyl or {(C1-6)alkyl-(C3-7)cycloalkyl}, which are all optionally substituted from 1 to 3 times with halo, cyano, nitro, O-(C1-6)alkyl, amido, amino or phenyl, or R1A is C6 or C10 aryl which is optionally substituted from 1 to 3 times with halo, cyano, nitro, (C1-6)alkyl, O-(C1 6)alkyl, amido, amino or phenyl; R2 is (C4-6)cycloalkyl; R3 is t-btuyl or (C5-6)cycloalkyl and R4 is (C4-6)cycloalkyl; or a pharmaceutically acceptable salt thereof. The compounds are useful as inhibitors of HCV NS3 protease for the treatment of Hepatitis C.

Abstract: A convenient and simple method for the synthesis of 1-methoxy-5,10-dioxo-5,10-dihydro-1H-benzo[g]isochromene-3-carboxylic acid (3-(dimethylamino)propyl)amide 4c was developed. The key step involves the easy formation of 1,3-disubstituted cyclic alkenyl ether, an important framework of isochromene natural products, with a dual role Pd(II) catalyst.

Abstract: A simple and efficient method has been developed for chemoselective deprotection of phenolic methoxymethyl (MOM) ethers using silica-supported sodium hydrogen sulfate as a heterogeneous catalyst. The conversions occur at room temperature, and the yields of the deprotected phenols are excellent. The method is suitable for deprotection of phenolic MOM ethers of multifunctional bioactive natural products.