Abstract: 3,4-Phenylenedioxythiophene (PheDOT), a benzenic analogue of 3,4-ethylenedioxythiophene (EDOT), has been synthesized using two different routes namely etherification of 2,5-dicarboethoxy-3,4-dihydroxythiophene with halo-aromatics and transetherification of 3,4-dimethoxythiophene with catechols. Quantum calculations and electrochemical measurements show that replacement of the ethylene bridge of EDOT by a phenyl group leads to an increase of the HOMO level and to a stabilization of the cation radical, making electropolymerization of PheDOT more difficult than that of EDOT. The synthesis of several PheDOT derivatives is described together with preliminary results on their electrochemical polymerization and on the properties of the resulting polymers and copolymers.

Abstract: A heat-sensitive lithographic printing plate precursor is disclosed which comprises a hydrophilic support and an oleophilic coating comprising an infrared absorbing agent and a polymer, which comprises a phenolic monomeric unit wherein the phenyl group of the phenolic monomeric unit is substituted by a group having the structure —N═N-Q wherein the —N═N— group is covalently bound to a carbon atom of the phenyl group and wherein Q is an aromatic group and wherein the substitution increases the chemical resistance of the coating.

Abstract: Low-temperature crystal growth was investigated in the fragile liquids of iso-propylbenzene, dimethylphthalate, diphenylphthalate, and 2-methyltetrahydrofuran by using an optical microscope. Homogeneous-nucleation-based (HNB) crystal growth was observed to proceed in the supercooled liquids of the former three substances around and below their glass-transition temperatures, as in the cases of o-terphenyl, toluene, and other fragile liquids, but not detected in 2-methyltetrahydrofuran. Thus far, the growth has been observed only for the substances possessing phenyl group(s) in the molecule. The maximum rates of the growth were found to decrease with increasing the size of substituents to the phenyl ring(s). It was concluded from this fact that the C–H⋯π(electron) intermolecular interaction between phenyl rings enhances to generate an ordered region required for the crystal nucleation and thereby the HNB crystal growth. Among all the observations of the HNB growth, a rough relation was found that the maximum growth rate increases with an increasing maximum-rate temperature normalized by the respective glass transition temperatures.

Abstract: Complex stability constant (K), standard free energy (ΔG°), reaction enthalpy (ΔH°), and entropy change (TΔS°) for 1:1 inclusion complexation of the diastereomeric dipeptides Z-d/l-Glu-l-Tyr (Z = benzyloxycarbonyl) and its component amino acids (Z-d/l-Glu and N-Ac-Tyr) with native α-, β-, and γ-cyclodextrins (CDs) and A,X-modified bis(6-trimethylammonio-6-deoxy)-β-CDs (AX-TMA2-β-CDs) were determined in buffer solution (pH 6.9) at T = 298.15 K by isothermal titration microcalorimetry. Concurrent NMR spectral examinations revealed that the penetration mode and the resulting complex architecture are dramatically altered by the peripheral modification and also by the CD's cavity size. Upon complexation of the ditopic Z-Glu-Tyr guest, native α- and β-CDs preferentially bind the Z's phenyl group, whereas AX-TMA2-β-CDs predominantly include the Tyr's phenol moiety. In contrast, native γ-CD includes both of the aromatic moieties simultaneously in the same cavity. Furthermore, for isomeric AB-, AC, and AD-TMA2-β-C...

Abstract: Photoswitching of the coordination number of silicon between four and five in allyldifluoro[2-(phenylazo)phenyl]silane, which was confirmed by X-ray analysis and multinuclear NMR spectroscopy, caused multistep reactions to proceed or stop, yielding tetrafluoro[2-(1-allyl-2-phenylhydrazino)phenyl]silicate without altering other reaction conditions.

Abstract: Two novel structures of adamantane-modified benzoxazines were synthesized from 4-(1-adamantyl)-phenol through the incorporation of adamantane as a pendant group into the polybenzoxazine backbone. Both 1H-NMR and Fourier transform infrared spectra were used to characterize these structures. The rigid structure of the adamantane tended to hinder the chain mobility (boat anchor effect) and substantially enhanced the thermal properties, including the glass-transition temperature and decomposition temperature, especially for poly(6-adamantyl-3-methyl-3,4-dihydro-2H-1,3-benzoxazine). In the poly(6-adamantyl-3-phenyl-3,4-dihydro-2H-1,3-benzoxazine) system, however, the opposite result for the glass-transition temperature was observed and it was interpreted as lower crosslinking density. The phenyl group was bulkier than the methyl group, and the movement of the molecular chain was hindered between bridging points during the curing process; this resulted in a lower crosslinking density and a lower glass-transition temperature than those of poly(6-adamantyl-3-methyl-3,4-dihydro-2H-1,3-benzoxazine). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 932–940, 2004

Abstract: In order to develop orally active CCR5 antagonists, we investigated 1-benzoxepine derivatives containing new polar substituents, such as phosphonate, phosphine oxide or pyridine N-oxide moieties, as replacements for the previoiusly reported quaternary ammonium moiety. Among these compounds, the 2-(α-hydroxybenzyl)pyridine N-oxide 5e exhibited moderate CCR5 antagonistic activity and had an acceptable pharmacokinetic profile in rats. Subsequent chemical modification was performed and compound (S)-5f possessing the (S)-configuration hydroxy group was found to be more active than the (R)-isomer. Replacement of the 1-benzoxepine ring with a 4-methylphenyl group by a 1-benzazepine ring with a 4-[2-(butoxy)ethoxy]phenyl group enhanced the activity in the binding assay. In addition, introduction of a 3-trifluoromethyl group on the phenyl group of the anilide moiety led to greatly increased activity in the HIV-1 envelope-mediated membrane fusion assay. In particular, compound (S)-5s showed the most potent CCR5 antagonistic activity (IC50=7.2 nM) and inhibitory effect (IC50=5.4 nM) in the fusion assay, together with good pharmacokinetic properties in rats.

Abstract: The synthesis and thermotropic properties of four homologous series of salicylaldimine-based dimer liquid crystals are reported. Two 4-(4-alkoxy-2-hydroxybenzylideneamino)benzoyloxy groups are connected to a central part consisting of a 1,3-phenylene, 1,5-pentylene, 2,2-dimethyl-1,5-pentylene or 3,3-dimethyl-1,5-pentylene unit. The terminal alkoxy chains have been varied from 4 to 16 carbon atoms in length. All the compounds exhibit liquid crystalline phases whose behaviour depends on the nature of the central part and the length of the alkoxy terminal chains. All compounds of the series with the central phenyl part exhibit enantiotropic B-phases, and the sequence B6–B1–B2 on increasing terminal chain length was observed. Replacement of the phenyl group with a pentyl central group partly suppresses the formation of B-phases. The longer homologues of this series show the B1 phase, while the shorter exhibit an intercalated SmCc mesophase. The introduction of methyl substituents to the pentyl spacer causes t...

Abstract: The synthetic flavylium salt 7-(N,N-diethylamino)-4′-hydroxyflavylium tetrafluoroborate gives rise in aqueous solution to a complex network of chemical reactions driven by pH. The system was studied by 1H NMR, single crystal X-ray diffraction, steady state and transient UV-Vis spectrophotometry as well as stopped flow. The crystal structure shows a high degree of coplanarity between the pyrylium system and the phenyl group in position 2. Thermodynamic and kinetic constants for the pH dependent network of chemical reactions were obtained. The introduction of an amino group in position 7 allows formation of protonated species leading, in particular, to a tautomeric form of the protonated cis-chalcone, CcH+, whose absorption spectra is rather red shifted, in comparison with the correspondent protonated trans-chalcone, CtH+. The CcH+ species can be rapidly converted into the flavylium cation through a first order process with lifetime of 0.2 s at pH = 2.35. This new reaction channel confers this compound a peculiar behaviour in acidic media, allowing to define an unidirectional pH driven reaction cycle.

Abstract: This invention provides a compound of the formula (I): wherein A represents a phenyl group or the like: B represents an aryl or the like: E represents a 1,4-phenylene group; R1 and R2 independently represent a hydrogen atom or the like: R3 and R4 independently represent a hydrogen atom or the like: R5 represents -CO2H or the like:R6 represents an alkyl group having from 1 to 6 carbon atoms or the like: X represents a methylene group or the like. These compounds are useful for the treatment of disease conditions mediated by prostaglandin such as pain, or the like in mammalian. The compounds act as antagonists of the prostaglandin E2 receptor. This invention also provides a pharmaceutical composition comprising the above compound.

Abstract: Phenyldimethylsilyllithium reacts with N,N-dimethylamides in a variety of ways, depending upon the stoichiometry, the temperature and, most subtly, on the structure of the amide, with quite small-seeming changes in structure leading to profound changes in the nature of the products. When equimolar amounts of the silyllithium reagent and N,N-dimethylamides 6 are combined in THF at −78 °C, and the mixture quenched at −78 °C, the product is the corresponding acylsilane 8. If the same mixture is warmed to −20 °C before quenching, the product is a cis enediamine 11. The enediamines are easily isomerised from cis to trans, easily oxidised to dienediamines 15, and, with more difficulty, hydrolysed to α-aminoketones 13. If two equivalents of the silyllithium reagent are used, the product is an α-silylamine 20. The mechanism of formation of the enediamines appears to be by way of a Brook rearrangement of the tetrahedral intermediate 17 followed by loss of a silanoxide ion to give a carbene or carbene-like species. The ‘carbene’ combines with the Brook-rearranging nucleophile to give an intermediate 28, which loses another silanoxide ion to give the enediamine. The same carbene can be attacked by a second equivalent of the silyllithium reagent to give the α-silylamine 20. Other nucleophiles, like alkyllithiums, phenyllithium, and tributylstannyllithium also trap the carbene to give products 48–52. The intermediate anions in these reactions, when benzylic, can be further trapped with alkylating agents to give the products 33, 34 and 53–55. In special cases, the anion formed by attack on the carbene can be trapped by intramolecular reactions displacing internal leaving groups, as in the formation of the enamine 37 and the cyclopentane 41, or attacking a carbonyl group, as in the formation of the indanone 61, or attacking a double or triple bond, as in the formation of the cyclopentanes 71 and 75. In another special case, the carbene reacts with vinyllithium to give an allyllithium intermediate 56, which selectively attacks another molecule of carbene to give eventually the γ-aminoketone 58. Small changes in the structure of the amide lead to a variety of other pathways each of which is discussed in the text. Notably, each member of the homologous series of amides Ph(CH2)nCONMe2 gives rise to a substantially different product: when n = 0, the reaction is normal, and the yield of the α-silylamine 20e is high; when n = 1, proton transfer in the intermediate anion 64 and displacement of the phenyl group leads to the silaindane 66; when n = 2, fragmentation of the intermediate anion 80, and capture of the carbene by benzyllithium leads to the 1,4-diphenylbut-2-ylamine 83; and when n = 3, proton transfer in the intermediate anion 67 and displacement of the phenyl group leads to the silacyclopentane 69.

Abstract: The present invention provides an antifungal agent represented by the formula: [wherein A1 represents a 3-pyridyl group which may have a substituent, a quinolyl group which may have a substituent, or the like; X1 represents a group represented by the formula —NH—C(═O)—, a group represented by the formula —C(═O)—NH—, or the like; E represents a furyl group, a thienyl group, a pyrrolyl group, a phenyl group, a pyridyl group, a tetrazolyl group, a thiazolyl group or a pyrazolyl group; with the proviso that A1 may have 1 to 3 substituents, and E has one or two substituents].

Abstract: To estimate the antimicrobial effect of p-hydroxyphenyl acrylate (H5) derivatives on the basis of their molecular structure, the hydroxy and acryl groups of p-hydroxyphenyl acrylate were modified. The antimicrobial activity of the resulting compounds was assessed against a Gram-positive bacterium (Staphylococcus aureus), a Gram-negative bacterium (Pseudomonas aeruginosa), and fungi (Aspergillus fumigatus and Penicillium pinphilum) by the halo zone and the shake flask test. The antimicrobial activity of H5 was ascribed mainly to the acryl group. Compounds with acryl or acryloxy groups bound to the phenyl moiety were found to exhibit particularly high antimicrobial activities. The activities of phenyl acrylate and phenyl vinyl ketone were excellent as compared to aliphatic acrylates such as cyclohexyl acrylate and hexyl acrylate, indicating that the stereoelectronic effect of the phenyl group was important to the antimicrobial activity.

Abstract: To control the molecular organization of octadecyl rhodamine B (RhB18), hybrid Langmuir–Blodgett monolayers containing clay minerals were prepared. The orientation and conformation of the RhB18 molecule were analyzed by polarized attenuated total reflection Fourier transform infrared (ATR–FTIR) spectroscopy and fluorescence spectroscopy. Monomers and dimers of RhB18 were observed by UV-Vis absorption spectroscopy. Infrared bands of RhB18 exhibited dichroism and shifted to higher or lower wavenumbers in films as a function of clay content. The main fluorescence band of RhB18 was more intense and shifted to lower wavelengths in films with higher clay content. In films without clay, the phenyl group of RhB18 is tilted relative to the xanthene group and both groups are tilted relative to the substrate. In films with clay, both the phenyl group and xanthene group are oriented parallel to the clay surface which is parallel to the substrate. The clay mineral surface induces a change in the conformation and orientation of the RhB18 chromophore.

Abstract: The invention relates to an improved process for the preparation of a macrocyclic compound of formula I wherein R 1 , R 2 , R 3 , A and D have the meaning given in the claims; by a ring closure metathesis of the corresponding diene of formula III wherein R 1 , R 2 , R 3 , A and D′ have the meaning given in the claims; in the presence of a benzylidene ruthenium catalyst, wherein the phenyl group is substituted by a nitro group

Abstract: The absolute configuration of β-amino alcohols and their ethers can easily be determined by comparison of the 1H NMR spectra of the mixture formed by the substrate amino alcohol or amino ether plus one equivalent of (R)-Boc–α-phenylglycine (BPG) with that of the mixture formed by the substrate plus one equivalent of (S)-BPG. Several examples of known absolute configuration have been used to validate the results, which are explained in terms of the selective shielding experienced by protons of the substrate located on the complex on the same side of the phenyl group of BPG. A graphical model has been proposed in which the use of the ΔδRS parameters for Cα–H, Cβ–H and the L group allow the direct configurational assignment from the NMR data.

Abstract: This invention provides a compound of the formula (I) wherein R1 and R2 independently represent a hydrogen atom or the like; X represents a covalent bond or the like: A represents a bicyclic, aromatic, saturated or partially unsaturated heterocyclic or carbocyclic group having from 8 to 12 ring atoms; or the like: B represents a phenyl group or a heteroaryl group having from 5 to 6 ring atoms or the like: These compounds are useful for the treatment of disease conditions caused by overactivation of NMDA NR2B receptor such of pain, or the like in mammalian This invention also provides a pharmaceutical composition comprising the above compound

Abstract: 1,1-Difluoroalk-1-enes bearing a phenyl group at the C-3, -4, or -5 position, readily obtained from 2,2,2-trifluoroethyl p-toluenesulfonate, are treated with FSO 3 H.SbF 5 to undergo Friedel-Crafts cyclization in (CF 3 ) 2 CHOH. The cyclization takes place via α-fluorocarbocations, followed by spontaneous hydrolysis of the C-F bond to afford bicyclic ketones including a five, six, or seven-membered ring in good yield.

Abstract: A method for treating plants in need of growth promotion, comprising applying to said plants, to the seeds from which they grow or to the locus in which they grow, a non-phytotoxic, effective plant growth promoting amount of an amide compound having the formula A-CO-NR1R2 in which A is an aryl group or an aromatic or non-aromatic, 5- or 6-membered heterocycle which has from 1 to 3 hetero atoms which are selected from O, N and S; where the aryl group or the heterocycle may or may not have 1, 2 or 3 substituents which are selected, independently of one another, from alkyl, halogen, CHF2, CF3, alkoxy, haloalkoxy, alkylthio, alkylsulfinyl and alkylsulfonyl; R1 is a hydrogen atom; R2 is a phenyl or cycloalkyl group which may or may not have 1, 2 or 3 substituents which are selected, independently of one another, from alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkenyl, cycloalkyloxy, cycloal- kenyloxy, phenyl and halogen, where the aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or the cycloaliphatic radicals may be substituted by from 1 to 3 alkyl groups and where the phenyl group may have from 1 to 5 halogen atoms and/or from 1 to 3 substituents which are selected, in dependently of one another, from alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and haloalkylthio, and where the amidic phenyl group may or may not be condensed with a saturated 5-membered ring which may or may not be substituted by one or more alkyl groups and/or may have a hetero atom selected from O and S.

Abstract: The invention relates to a substituted-pyrimidone derivative represented by formula (I) or a salt thereof, wherein: X represents two hydrogen atom, a sulfur atom, an oxygen atom or a C1-2 alkyl group and a hydrogen atom; Y represents a bond, a carbonyl group, a methylene group optionally substituted; R1 represents a 2, 3 or 4-pyridine ring or a 2, 4 or 5-pyrimidine ring, the rings being optionally substituted; R2 represents a phenyl group or a naphthalene ring; the phenyl group and the naphthalene ring being optionally substituted; R3 represents a hydrogen atour or a C1-6 alkyl group; R4 represents a C1-2 perhalogenated alkyl group or a C1-3 halogenated alkyl group; R5 represents a hydrogen atour; a C1-6 alkyl group or a halogen atom; n represents 0 to 3; and p+q=0 to 3. The invention relates also to a medicament comprising the said derivative or a salt thereof as an active ingredient which is used for preventive and/or therapeutic treatment of a neurodegenerative disease caused by abnormal activity of GSK3β, such as Alzheimer disease.