Studies on antiallergic agents. I. Synthesis and antiallergic activity of novel pyrazine derivatives.

Various pyrazine derivatives were synthesized and their antiallergic activity was examined. The inhibitory activity on allergic histamine release of the compounds bearing a 5-tetrazolyl group was more potent than that of the corresponding carboxyl derivatives. The introduction of -CONH- or -NHCO- between the pyrazine ring and the 5-tetrazolyl group as a spacer greatly enhanced the activity. N-(1H-Tetrazol-5-yl)-2-pyrazinecarboxamide (I-3) was estimated to exhibit nearly the same potency as disodium cromoglycate (DSCG). The structure-activity relationship among various derivatives modified by introducing some substituents onto the 3-, 5- or 6-position of the pyrazine ring of I-3 was investigated. The activity remained unchanged or was reduced when such substituents as methyl, chloro, methoxy, methylamino and dimethylamino were introduced at the 3- or 5-position. In contrast, 6-substitution with various alkylamino groups more or less increased the activity. Among them, the 6-dimethylamino (I-17c) and 6-(1-pyrrolidinyl) (I-34) derivative were proved to be most potent. The IC50 values (concentration which produces 50% inhibition of the allergic histamine release) of I-17c and I-34 were determined to be 4.7 x 10(-10) and 4.6 x 10(-10) M, respectively. These two compounds produced a potent inhibitory activity on passive cutaneous anaphylaxis (PCA) in rat, not only by the intravenous route (ED50 = 0.0096 mg/kg for both compounds) but also by the oral route (ED50 = 0.19 and 0.18 mg/kg, respectively). On the other hand, when the pyrazine ring of some representative compounds was replaced with a pyridine ring, the inhibitory activity on histamine release was significantly reduced.     

Evaluation of image sticking property on liquid crystal displays with polymer layers produced from phenanthrene-carrying monomers

As a model of polymer-sustained-alignment liquid crystal display (PSA-LCD), the liquid crystal (LC) cells having the polymer layers produced from monomers of phenanthrene (Phen)-carrying monomers, 2,7-, 3,8-, 1,8- and 3,6-dimethacryloyl-oxy-phenanthrene (DMAPhen), were prepared and investigated image sticking phenomenon with evaluations of residual direct current voltage (V_rDC) and difference in pretilt angle before and after application of alternate current voltage (Δtilt). The V_rDC values were small for the LC cells with the polymer layers produced from the Phen-carrying monomers used in this study. On the other hand, Δtilt depends on the molecular structure of the Phen-carrying monomer. The Δtilt values became small with increasing the linearity of the monomer structure for the Phen-carrying monomers. The findings would be useful for obtaining the small level of image sticking in the PSA-LCDs produced from the Phen-carrying monomers.     

Vacancies in the solids of low molecular weight organic compounds observed by positron annihilation

PAL were measured for several low molecular organic compounds, normal and cyclic-hydrocarbons and their perfluorinated ones, from room temperature down to about 40 K, and information about the vacancies in them has been extracted from ₃ andI ₃. Normally the size of vacancies were larger in the solids comprising larger molecules, showing thato-Ps can represent the vacancy size. In a special case of perfluorocyclohexane whose solid had to be prepared by sublimation the vacancy size was larger than expected. In all the solid molecules studied twoo-Ps states could be observed and their relative importance could easily change showing a hysteresis-like behavior. At further lower temperatures of around 40 K theo-Ps state with longer lifetime and larger intensity became overwhelming for all molecules. Also ₃ andI ₃ were not very sensitive to most of the phase transitions, including the melting points.     

Production of submicron-sized multihollow polymer particles by alkali/cooling method

Submicron-sized styrene-methacrylic acid copolymer particles, which were produced by emulsion copolymerization, were changed to those having multihollow structure by treating stepwise the emulsion as follows. First alkali treatment was carried out at higher temperature than the glass transition temperature and subsequently the emulsion was cooled by keeping it at room temperature. This was named alkali/cooling method. The effects of methacrylic acid content, pH, time and temperature in the alkali treatment on the formation of multihollow structure were clarified.Part CLV of the series Studies on suspension and emulsion     

Alkane Oxidation with Molecular Oxygen Using a New Efficient Catalytic System: N-Hydroxyphthalimide (NHPI) Combined with Co(acac)(n)() (n = 2 or 3)

A novel class of catalysts for alkane oxidation with molecular oxygen was examined. N-Hydroxyphthalimide (NHPI) combined with Co(acac)(n)() (n = 2 or 3) was found to be an efficient catalytic system for the aerobic oxidation of cycloalkanes and alkylbenzenes under mild conditions. Cycloalkanes were successfully oxidized with molecular oxygen in the presence of a catalytic amount of NHPI and Co(acac)(2) in acetic acid at 100 degrees C to give the corresponding cycloalkanones and dicarboxylic acids. Alkylbenzenes were also oxidized with dioxygen using this catalytic system. For example, toluene was converted into benzoic acid in excellent yield under these conditions. Ethyl- and butylbenzenes were selectively oxidized at their alpha-positions to form the corresponding ketones, acetophenone, and 1-phenyl-1-butanone, respectively, in good yields. A key intermediate in this oxidation is believed to be the phthalimide N-oxyl radical generated from NHPI and molecular oxygen using a Co(II) species. The isotope effect (k(H)/k(D)) in the oxidation of ethylbenzene and ethylbenzene-d(10) with dioxygen using NHPI/Co(acac)(2) was 3.8.     

Hydrogen Effect on Coke Removal and Catalytic Performance in Pre-Carburization and Methane Dehydro-Aromatization Reaction on Mo/HZSM-5

1. Introduction As an effective utilization of methane, the methane dehydro-aromatization was focused in the last decade [1-28]. Over the Mo/HZSM-5 bi- functional catalyst at high reaction temperature, methane can be converted into light aromatics (ben- zene and naphthalene) and hydrogen. Mo active species can activate the C—H bond of methane; and HZSM-5 supplies the acid sites for the oligomeriza- tion and cyclization of hydrocarbons to form aromat- ics, and suppresses the deeper condens…     

Triple hydrogen bonds direct crystal engineering of metal-assembled complexes: the effect of a novel organic-inorganic module on supramolecular structure

Novel triply hydrogen bonded suprastructures based on [M(tdpd)2(L)2]2- (H2tdpd=1,4,5,6-tetrahydro-5,6-dioxo-2,3-pyrazinedicarbonitrile, L=solvent) and melamine-analogous cations have been synthesized and characterized. The use of anions containing two AAA sets from [M(tdpd)2(L)2]2- together with cations containing one DDD set (A=hydrogen-bond acceptor, D=hydrogen-bond donor) leads to the formation of complementary triply hydrogen bonded modules in the solid state. In all cases, the building module is further extended via additional hydrogen-bonding interactions to produce a tape, and tapes are assembled into sheets. These results show that a hydrogen-bonded module consisting of different kinds of building blocks, one of which is a metal complex that includes hydrogen-bond acceptor sites and the other is a hydrogen-bond donor molecule, will be attractive for constructing metal-containing supramolecular systems by the self-assembly technique.