Abstract: Bridged bicyclic lactams that incorporate the lactam nitrogen at a bridgehead position have been of interest for many years because they incorporate a “twisted amide” unable to achieve standard planar geometry.1 Although much of the work devoted to these compounds has focused on the hyperreactivity of the amide bond toward hydrolysis, recent work by us2 and others3 suggests that there is still much to be learned about the reactivity of these interesting structures. Not surprisingly, the tendency of these compounds to undergo rapid hydrolysis has complicated their synthesis. Although standard methods for amide bond formation have been used, such routes often proceed in poor yields or are accompanied by difficulty in product isolation.1 In this paper, we describe a solution to the problem of bridged bicyclic lactam synthesis that utilizes the acid-promoted reaction of an alkyl azide and a ketone4 in which the regiochemistry is controlled by a through-space interaction of an aryl group with a cationic leaving group in a key reaction intermediate. The utility of the intramolecular Schmidt reaction to the problem of bridged lactam was recently reported by Stoltz and Tani (Scheme 1a).5 Using 3-(azidoethyl)cyclopentanone, it proved possible to form a mixture of two lactams from which the desired quinuclidone 1a was isolated by recrystallization. This sequence is noteworthy because it permitted the isolation and characterization of the iconic bridged lactam 1a for the first time and also demonstrated the loss of N2 as a powerful driving force for the formation of this unstable ring system. Scheme 1 The placement of the azide-containing side chain at a carbon non-adjacent to the ketone means that only bridged lactams are possible in this reaction. For the analogous α-substituted ketones, however, two regiochemical outcomes can be envisioned (Scheme 1b). Such reactions almost always afford fused lactam by formal insertion of the azide into the proximal C–C bond of the reactive ketone (path a).4 We wished to obtain a new class of bridged lactams2 that would be formed by the regiochemical alternative ring expansion via path b. The first example of an intramolecular Schmidt reaction to afford such a bridged bicyclic lactam was encountered unexpectedly (Scheme 2).6,7 Thus, triene 2 underwent an intramolecular Diels–Alder reaction to afford a ketone that further reacted to give a mixture of the expected fused lactam 3a and a bridged isomer 3b. We propose that the regiochemistry of the Schmidt reaction involves the selective migration of the C–C bond antiperiplanar to the leaving N2+ substituent. In this scenario, chairlike cyclohexanones can only afford a bridged lactam when the azide-containing side chain occupies a pseudoaxial orientation (see the Supporting Information for details of this published argument4). Once this condition is satisfied, then antiperiplanar migration of the C–C bond anti to the equatorial N2+ group in A would afford the fused isomers whereas the axially disposed leaving group in B is necessary for the formation of the bridged isomers. Scheme 2 We first attempted to affect this equilibrium by disfavoring isomer A through the placement of a bulky group at R2. To this end, the isopropyl-containing isomer 4 was synthesized and submitted to Lewis acid treatment. In this case, essentially the same ratio of bridged/fused adducts was obtained. Conversely, the analog bearing a phenyl group at the same position gave a dramatically different result. In this case, compound 7a was formed as a single isomer in 85% yield, making this reaction the most efficient example of this sequence observed to date. Although the two substituents are similar in A values,8 we wondered if the apparently exclusive intermediacy of A might be explained by an attractive through-space interaction between the positively charged leaving group and the phenyl group. Although commonly invoked in small molecule/protein binding interactions,9 such cation–π interactions have only occasionally been proposed in stereoselective synthesis.10 In one case, we proposed such an interaction as a controlling feature of certain asymmetric Schmidt reactions.11 Accordingly, we hypothesized that an appropriately situated aromatic group might be able to stabilize isomer B and provide a direct route to bridged isomers. Control experiments demonstrated that neither placement of a phenyl group at the α carbon (entry 1) nor the axial orientation of the side chain (entry 2) alone is sufficient to steer the reaction toward fused lactam product (although the small amounts of 10b are consistent with the results seen in Scheme 212). However, the combination of an axial azide-containing tether and an aromatic group in a 1,3-diaxial relationship with the leaving N2+ group in the intermediate azidohydrin diverts the reaction so that bridged product predominates. The fact that the ratio of bridged to fused isomers increases with a more electron-rich aromatic group provides strong support that a 1,3 cation–π effect is in play (cf. entries 3 and 4). The relevant intermediates are shown in Scheme 3. Our hypothesis is supported by several observations. First, the fact that 8a affords only fused product 9a rules out any effect arising from differences in intrinsic migration aptitudes. In this case, the thermodynamically favored conformation of 8a affords a reactive intermediate that can only lead to 9a. Interestingly, the alternative conformation bearing an axial side chain, that could in principle lead to bridged isomer, does not appear to react in this example (although it very likely exists in the ground state). The effect of phenyl group placement in compounds 8b–d is depicted in the bottom part of Scheme 3. Scheme 3 Overall, these results indicate an important role for stereoelectronic effects in controlling the regiochemistry of this reaction. The fact that the vast majority of 2-azidoalkyl ketones undergo rearrangement to afford fused lactams may reflect both the conformation of the reactive intermediate azidohydrin and the stability of normal vs. twisted lactams. In particular, the observation of a small amount twisted amide from compound 8b indicates that appropriately constrained compounds can lead to bridged isomers, if only as minor products. However, the observation of through-space control of these intramolecular Schmidt reactions is especially provocative. This laboratory will carry out further investigations of this interesting effect in this chemistry and in other contexts as well.

Abstract: A series of C5-substituted 1,2,4-triaryl-1H-imidazoles was synthesized. Their gene-activating properties were determined on estrogen receptor alpha positive MCF-7 breast cancer cells, stably transfected with the plasmid EREwtcluc (MCF-7-2a cells). The influence of 4-OH and 2-Cl substituents on the phenyl rings as well as the significance of a methyl, ethyl, or phenyl group at C5 on the estrogen receptor binding and the resulting gene activation in MCF-7-2a cells was studied. The alkyl and aryl groups at C5 of 1,2,4-tris(4-hydroxyphenyl)-1H-imidazole 1 increased the transactivation, while chlorine atoms on the phenyl rings diminished this effect. 5-Ethyl-1,2,4-tris(4-hydroxyphenyl)-1H-imidazole 9 was identified as the most active compound. Its excellent transcriptional activity did not only depend on the C5 ethyl group, but also on the three hydroxyl groups of the phenyl rings. Compounds (11-14) with a reduced number of hydroxyl groups displayed distinctly lower gene activation.

Abstract: Azo−hydrazone tautomerism in azo dyes has been modeled by using density functional theory (DFT) at the B3LYP/6-31+G(d,p) level of theory. The most stable tautomer was determined both for model compounds and for azo dyes Acid Orange 7 and Solvent Yellow 14. The effects of the sulfonate group substitution and the replacement of the phenyl group with naphthyl on the tautomer stability and on the behavior in solvent have been discussed. Intramolecular hydrogen bond energies have been estimated for the azo and hydrazone tautomers to derive a relationship between the tautomer stability and the hydrogen bond strength. The transition structures for proton transfer displayed resonance assisted strong hydrogen bonding properties within the framework of the electrostatic-covalent hydrogen bond model (ECHBM). Evolution of the intramolecular hydrogen bond with changing structural and environmental factors during the tautomeric conversion process has been studied extensively by means of the atoms-in-molecules (AIM) ana...

Abstract: PROBLEM TO BE SOLVED: To provide a new photopolymerization initiator carrying out curing with a small addition amount and a little photoirradiation energy, and capable of suppressing the volatilization and the generation of smell of the photopolymerization initiator and a decomposed product of the photopolymerization initiator generated from a polymerizable composition after the curing, and to provide the polymerizable composition using the photopolymerization initiator. SOLUTION: The basic skeleton of the structural formula of the photopolymerization initiator includes a specific structure including a phenylcarbazole (the phenyl group may have a substituent such as a hydrogen atom, a halogen atom, a nitro group, a cyano group, a haloalkyl group, or an acyl group) at the center, and amino groups at the 5 and 10 positions of the carbazole group through a ketone group and carbon (the carbon has a substituent such as an alkyl group, an aryl group or a heterocyclic group, and the amino group has a substituent such as a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group). COPYRIGHT: (C)2010,JPO&INPIT

Abstract: A large sized thin-walled shaped article having a complicated shape can be realized by improving fluidity at the time of shaping without deterioration of the intrinsic characteristic properties of an aromatic polycarbonate resin, namely, transparency, resistance to exfoliation of surface layer, thermal resistance, impact resistance, and chemical resistance. Specifically disclosed is a fluidity-improving agent containing 0.5 to 99.5 parts by mass of a polymer (A) which is obtained by polymerizing a monomer mixture (a) containing 0.5 to 99% by mass of (a1) an aromatic vinyl monomer, 0.5 to 99% by mass of (a2) a phenyl(meth)acrylate or a phenyl(meth)acrylate having a substituent in a phenyl group, and 0.5 to 5% by mass of (a3) a vinyl monomer having a functional group (X), and 0.5 to 99.5 parts by mass of a polymer (B) which is obtained by polymerizing a monomer mixture (b) comprising (b1) a phenyl (meth)acrylate or a phenyl (meth)acrylate having a substituent in a phenyl group with a compound having a functional group (Y) capable of reacting with the functional group (X), with the proviso that a total of the polymer (A) and the polymer (B) is 100 parts by mass.

Abstract: The present invention provides a compound represented by the formula (I): or a pharmacologically acceptable salt thereof, wherein Ar1 represents an imidazolyl group that may be substituted with a C1-6 alkyl group, or the like, Ar2 represents a phenyl group that may be substituted with a C1-6 alkoxy group, or the like, X1 represents a double bond or the like, and Het represents an imidazolyl group that may be substituted with a C1-6 alkyl group, or the like, which is effective as a therapeutic or prophylactic agent for a disease caused by Aβ.

Abstract: Density functional theory calculations have been performed to elucidate the factors that influence the regioselectivity of toluene hydroxylation by a model of the active species of cytochrome P450 enzymes, so-called Compound I (Cpd I). Cpd I can hydroxylate the benzylic C–H and generate benzyl alcohol, or it can activate the phenyl group and produce p-cresol and p-methylcyclohexanone products. The reactions take place via two-state reactivity on competing doublet and quartet spin state surfaces. In the gas phase, the benzyl alcohol is preferred over p-cresol by more than three orders of magnitude. Environmental perturbations, namely, NH···S hydrogen bonding to the thiolate ligand and bulk polarity of the protein, lower this preference to roughly 10:1 in favour of benzyl alcohol. Substitution of methyl hydrogen atoms by deuterium atoms raises the barriers that lead to benzyl alcohol without affecting those leading to p-cresol. Therefore combining toluene deuteration with the effects of NH···S hydrogen bonding and bulk polarity lowers the free energy difference between the two processes to only 0.4 kcal mol–1, and the two processes become competitive. These results as well as the calculated kinetic isotope effects are in good general agreement with experimental data. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Abstract: Molecular catalysts for organic synthesis should be constructed to be tailored to target reactions and their desirable conditions In our search for them, we have studied new types of transition metal molecular catalysts dressed with a tridentate N,C,N modular ligand, which consists of a C2-symmetric side-by-side phenyl group with chiral bis(oxazolinyl) substituents The ligand, 2,6-bis(oxazolinyl)phenyl abbreviated as Phebox, can connect covalently to transition metals by the central carbon atom Here, we review our recent work on the chemistry of Phebox and its metal complexes, including preparation, structural analysis, asymmetric Lewis acid catalysis, asymmetric hydrosilylation, asymmetric conjugate reduction, asymmetric reductive aldol reaction, and organometallic reactions © 2007 The Japan Chemical Journal Forum and Wiley Periodicals, Inc Chem Rec 7: 159–166; 2007: Published online in Wiley InterScience (wwwintersciencewileycom) DOI 101002/tcr20114

Abstract: Disclosed are a novel hydrogen storage material with enhanced hydrogen storage capacity prepared by doping an organic framework material with light metal cations, and a method of using the same for hydrogen storage. The present inventive material has at least one phenyl group at each face of a triangular building unit, which is doped with metal cations such as alkali metal cations, alkali-earth metal cations, etc., so that the material exhibits greatly improved capacity of hydrogen absorption and desorption at room temperature and can provide hydrogen storage materials practically adapted for fuel batteries useable even at room temperature.

Abstract: Disclosed is a novel 1,2-dihydroquinoline derivative represented by the general formula (1) below, which has a substituted phenylamino lower alkyl group and a phenyl group having an ester structure introduced therein as substituents, or a salt of such a derivative. The compound (1) or a salt thereof is useful as a glucocorticoid receptor modulator. In the formula below, R1 represents a hydrogen atom or a lower alkyl group; R2 represents a hydrogen atom or a lower alkyl group; R3 and R4 may be the same or different and represent a hydrogen atom or a lower alkyl group; R5 represents a hydrogen atom or a lower alkyl group; R6 represents a halogen atom, a lower alkyl group, a hydroxy group, a lower alkoxy group, a nitro group or a cyano group; X represents -C(O)-, -C(O)NR8-, -S(O)2- or the like; R7 and/or R8 may be the same or different and represent a hydrogen atom, an optionally substituted lower alkyl group, an optionally substituted aryl group, an optionally substituted heterocyclic group, an optionally substituted lower alkoxy group or the like; Y represents a lower alkylene group; and p represents 0, 1, 2 or 3.

Abstract: The absorption and fluorescence properties of nifedipine (NPDHP), felodipine (CPDHP) and a series of structurally related 1,4-dihydropyridines were studied in aqueous solution and organic solvents of different properties. The absorption and fluorescence spectra were found to depend on the chemical nature of the substituents at the position 4 of the 1,4-dihydropyridine ring (DHP) and on solvent properties. In aqueous solution, the fluorescence spectra of 4-phenyl substituted compounds are blue-shifted with respect to the alkyl substituted compounds. The more fluorescent compound is CPDHP. Nifedipine is not fluorescent. All compounds, with the exception of CPDHP, present monoexponential fluorescence decay with very short lifetime (0.2-0.4 ns). CPDHP showed a biexponential emission decay with a long-lived component of 1.7 ns; this behavior is explained in terms of different conformers because of the hindered rotation of the phenyl group by the ortho-substitution. Analysis of the solvent effect on the maximum of the absorption spectrum by using the linear solvent-energy relation solvato-chromic equation indicates the redshifts are influenced by the polarizability, hydrogen bonding ability and the hydrogen bond acceptance of the solvent. Whereas, the fluorescence characteristics (spectra, quantum yields and lifetimes) are sensitive to the polarizabilty and hydrogen bond ability of the solvents. Photo-decomposition of nifedipine is dependent on the solvent properties. Faster decomposition rates were obtained in nonprotic solvents. The 4-carboxylic derivative goes to decarboxylation. Under similar conditions, the other DHP compounds did not show appreciable photodecomposition.

Abstract: The present invention relates to a compound, useful as a mineralocorticoid receptor-modulating agent, of the following formula [I]: wherein Ring A is a benzene ring optionally having a substituent(s) other than R1 etc, R1 is a group of the formula: RaSO?2#191NH- etc, Ra is an alkyl group etc, R2 and R3 are each a hydrogen atom, a phenyl group, an optionally substituted alkyl group etc, X is an oxygen atom etc, Y is a group of the formula: -C(=O)- etc, Ar is an optionally substituted aryl group or an optionally substituted heteroaryl group, Q is a single bond, an alkylene group etc, or a pharmaceutically acceptable salt thereof.

Abstract: trans-Stilbene (t-St) is incorporated as an intact molecule without solvent in the medium size channel of nonacidic aluminum rich Na6.6ZSM-5 zeolite with Na6.6(SiO2)89.4(AlO2)6.6 formula per unit cell. The interaction between Na+ cation and t-St occurs through one phenyl group facially coordinated to the Na+ cation near the O atoms binding Al atoms. The similarity between Raman spectra of t-St in solution and occluded in Na6.6ZSM-5 shows that the motion of t-St in the channel approaches at room temperature the isotropic limit characteristic of a liquid. The laser UV (266 nm) photoionization generates a primary t-St•+-electron pair as a fast phenomenon. These charge carriers exhibit lifetimes that extend over less than 1 h at room temperature and disappear according to two parallel competitive ways: direct charge recombination and electron transfer. This subsequent electron-transfer takes place between the electron deficient radical cation (t-St•+) and the electron donor oxygen atom of the zeolite framewo...

Abstract: Glycine adsorbed on Cu(110) forms (marginally) heterochiral (3 × 2) reconstructed overlayers, in contrast to phenylglycine preferring homochiral adsorption. Density-functional theory within generalized gradient approximation is used to identify the origin of this difference. We find the restriction of the molecular relaxation imposed by the phenyl group in conjunction with intermolecular hydrogen bonds to be responsible.

Abstract: PROBLEM TO BE SOLVED: To provide a paddy field herbicide having selectivity between weed grasses and crop plants. SOLUTION: A novel haloalkylsulfonanilide derivative represented by general formula (I) awherein R 1 represents a halo(C 1 -C 8 ) alkyl group; R 2 represents an alkyl group, an alkenyl group, an alkynyl group, a phenylalkyl group, a phenylcarbonylalkyl group, an alkoxyalkyl group, a phenylalkoxy(C 1 -C 6 ) alkyl group, a heterocyclic alkyl group or the like; R 3 and R 4 individually represent H, an alkyl group, a cycloalkyl group, a halogen atom, CN or the like with R 3 and R 4 forming a 3 to 7 membered ring; R 5 , R 6 , R 7 and R 8 individually represent H, a halogen atom, an alkyl group, an alkoxyalkyl group, a phenyl group, a heterocycle, an alkylaminocarbonyl group, OH, CN or the like; A and W individually represent O or S; X represents one to four substituent(s) which may be the same or different and selected from H, a halogen atom, an alkyl group, a haloalkylsulfinyl group, an alkylsulfonyl group, a phenyl group, a phenoxy group, a phenylalkylaminocarbonyl group, OH, CN and the like} and a salt thereof are disclosed. A herbicide comprising the novel haloalkylsulfonanilide derivative or a salt thereof is disclosed. COPYRIGHT: (C)2008,JPO&INPIT

Abstract: Disclosed is a compound represented by the formula (I) below or a pharmacologically acceptable salt thereof. Also disclosed is a use of the compound or salt as a pharmaceutical product. (In the formula, Ar1 represents an imidazolyl group which may be substituted with a C1-6 alkyl group; Ar2 represents a phenyl group which may be substituted with a C1-6 alkoxy group; X1 represents a single bond; R1 and R2 respectively represent a C1-6 alkyl group or the like which may be substituted with a substituent such as a 5- to 14-membered aromatic heterocyclic group; and R3 represents a hydrogen atom or the like.)

Abstract: A process for preparing a compound of the formula IA or IB, wherein R is a!kyl, aminoalkyl, halogenalkyl, aralkyl, cycloalkyl, cycloalkylalkyl, alkoxy, phenyl or substituted phenyl or pyridyl group; the term alkyl means carbon chain, straight or branched, containing from 1 to 18 carbon atoms; the term halogen represents fluorine, chlorine, bromine or iodine; the term cycloalkyl represents a saturated alicyclic gτoup with 3 to 6 carbon atoms; the term aryl represents unsubstituted phenyl group or phenyl substituted by alkoxy, halogen or nitro group, the process comprising asymmetric hydrogenation of a compound of the formula II, wherein R has the same meanings as above, using a chiral catalyst and a source of hydrogen.

Abstract: The invention relates to derivatives of imidazopyridine 2-carboxamides, having general formula (I), in which: X represents an optionally substituted phenyl group; R1 represents a hydrogen atom, a halogen, a (C1-C6)alkoxy group, a (C1-C6)alkyl group, a (C3-C7)cycloalkyl(C1-C6)alkyl group, a (C3- C7)cycloalkyl(C1-C6)alkoxy group, an amino, a NRcRd group, whereby the alkyl and alkoxy groups can be optionally substituted; R2 represents a hydrogen atom, an optionally substituted (C1-C6)alkyl group, an optionally substituted (C1-C6)alkoxy group, a (C3-C7)cycloalkyl(C1- C6)alkyl group, a (C3-C7)cycloalkyl(C1-C6)alkoxy group, a (C2- C6)alkenyl group, a (C2-C6)alkynyl group, a -CO-R5 group, a -CO- NR6R7 group, a -CO-O-R8 group, a -NR9-CO-R10 group, a -NR11R12 group, a halogen atom, a cyano group or an optionally substituted phenyl group; R3 represents a hydrogen atom, a (C1-C6)alkyl group, a (C1-C6)alkoxy group or a halogen atom; and R4 represents a hydrogen group, a (C1-C4)alkyl group, a (C1-C4)alkoxy group or a fluorine atom. The invention also relates to the preparation method thereof and to the use of same in therapeutics.

Abstract: We report a computational investigation of the conformation and the dynamics of self-assembled monolayers (SAMs) of a set of aromatic thiols arranged in the (√3 × √3)-R30° packing ratio on a Au(111) surface using molecular dynamics (MD) simulations. It was found that the molecular conformations were better defined for the arylthiol with two phenyl groups as compared to those with a single phenyl group and that the chemical structure of the head and tail groups had a considerable influence on the system geometry. In line with the density functional theory (DFT) calculations of small thiol molecules, we found for the SAMs that the face-centered cubic (fcc) site on the Au(111) surface was the most preferred, followed by the hexagonal close-packed (hcp) site, while the bridge position showed the characteristics of a local energy maximum. The dynamics of thiol head groups on these three Au sites was found to govern the overall dynamics of SAMs as measured by the mean square displacement. We also report that bo...

Abstract: Provided is a curable silicone rubber composition, including: (A) an organopolysiloxane containing two or more silicon atom-bonded aliphatic unsaturated groups within each molecule, and containing a phenyl group and/or cyclohexyl group, (B) an organopolysiloxane resin with a three dimensional network structure consisting essentially of Q units and M units, and containing one or more phenyl groups and/or cyclohexyl groups, (C) an organohydrogenpolysiloxane, and (D) a platinum group metal-based catalyst, in which the component (B) exists in a quantity that represents from 20 to 80% by mass of the combination of the component (A) and the component (B), and in the component B, the quantity of low molecular weight substances, for which the weight average molecular weight measured by GPC and calculated against polystyrene standards is not greater than 500, is not greater than 5% The composition is capable of forming a cured product with improved hardness, no surface tackiness, a high refractive index, and excellent resistance to thermal shock, without any loss in rubber-like properties such as elongation