Reaction of 3-acetonyl-5-cyano-1,2,4-thiadiazole with phenylhydrazine hydrochlorides: indolization and phenylpyrazolation

Treatment of 3-acetonyl-5-cyano-1,2,4-thiadiazole (1) with 4-methyl or 4-methoxyphenylhydrazine hydrochloride provided 5-cyano-3-(2,5-dimethylindol-3-yl)-1,2,4-thiadiazole (2) or 5-cyano-3-(5-methoxy-2-methylindol-3-yl)-1,2,4-thiadiazole (3) as the sole product, respectively. In contrast, treatment of 1 with phenylhydrazine hydrochloride resulted in the formation of 5-cyano-3-(2-methylindol-3-yl)-1,2,4-thiadiazole (4) and the unexpected 5-cyano-3-(3,5-dimethyl-1-phenylpyrazol-4-yl)-1,2,4-thiadiazole (5). In a similar manner, when 1 was treated with 4-chlorophenylhydrazine hydrochloride, indolization was suppressed by phenylpyrazolation giving rise to 5-cyano-3-(5-chloro-2-methylindol-3-yl)-1,2,4-thiadiazole (6) and 5-cyano-3-[1-(4-chlorophenyl)-3,5-dimethylpyrazol-4-yl]-1,2,4-thia diazole (7). The reaction mechanism is discussed. Compounds 4, 5 and 6 exhibited weak antimicrobial activity against Helicobacter pylori.     

Direct polyesterification with thionyl chloride in pyridine improved by a modification of monomer sequences in copolymers

The direct polyesterification with thionyl chloride (SOCl₂) in pyridine was further investigated. Copolycondensations of dicarboxylic acids, bisphenols, and hydroxybenzoic acids were significantly affected by the reaction temperatures and combinations of monomers which could change relative rates of alcoholyses of the activated dicarboxylic acids and the hydroxyacids consequently to vary monomer sequences in the copolymers resulted. The sequences were tried to be varied more directly by stepwise reactions of monomers in copolycondensations of dicarboxylic acids, bisphenols, and p-hydroxybenzoic acid (PHB), as well as PHB and m-hydroxybenzoic acid (MHB). The reactions proceeded smoothly and satisfactorily when carried out by initial reaction of dicarboxylic acids and PHB followed by bisphenols likely to favor sequential to random distributions of monomers. Reverse addition of PHB and bisphenols, and then dicarboxylic acids resulted in rapid precipitation due to some oligomerization of PHB at an earlier stage of reaction, and largely retarded the reaction. This was also the case for the copolycondensation of PHB and MHB. Copolymers of high inherent viscosities with up to 65 mol% PHB could be obtained by initial reaction of MHB followed by PHB.     

A simplified optical method for measuring residual stress by rapid cooling in thermosetting resin strip

This paper presents a simplified optical method for measuring the residual stresses by rapid cooling in thermosetting resin strips. First, the fundamental equations for calculating the residual stress from the residual birefringence were obtained by the linear photoviscoelastic theory. The specimens were then subjected to rapid cooling. After rapid cooling, the residual stress was measured by two methods, the simplified optical method mentioned above and the well-known layer-removal method. The effectiveness of the simplified optical method was discussed by comparing results of the two methods.     

Halogen Selectivity in Nickel Salt-Catalyzed Cross-Coupling of Aryl Grignard Reagents with Bromochlorobenzenes a Novel Synthetic Method of Unsymmetrical Terphenyl

The reactions of aryl Grignard reagents with p- and m-bromochlorobenzenes catalyzed by non-ligated NiCl₂ give selectively chlorobiphenyl derivatives. By the stepwise reaction, an unsymmetrical terphenyl was synthesized in a good yield.     

Single chain distribution analysis near a substrate using a combined method of three-dimensional imaging and SCF simulation

The effect of preferential wetting of one of the constituent block chains and corresponding block copolymer morphologies to a carbon substrate is studied from a molecular level. The single chain distribution of the block copolymer was estimated as a function of the distance from the substrate by a combined method of transmission electron microtomography (TEMT) and self-consistent field (SCF) simulation. The former provides three-dimensional (3D) morphological information of cylindrical microdomains near the surface, while the latter utilizes the 3D morphology to quantitatively determine the interaction between the block chains and substrate, which is further used to estimate the single chain distribution of one of the block chains, i.e., the subchain, of the matrix. It was found that the subchains in the vicinity of the wetting layer are substantially compressed, while the radius of gyration of the subchain at a distance L (L is the interlayer distance of the cylindrical microdomains from the substrate) has already reached the same value as that in the bulk, indicating that the propagation of the surface interaction is limited to one layer. The methodology developed in this study can be used not only to estimate the surface effect on polymer chains for a variety of different surfaces, but also to provide a means to understand complicated block copolymer morphologies from a molecular level.     

Synthesis and antitumor activity of novel pyrimidinyl pyrazole derivatives. II. Optimization of the phenylpiperazine moiety of 1-[5-methyl-1-(2-pyrimidinyl)-4-pyrazolyl]-3-phenylpiperazinyl-1-trans-propenes

A series of novel 3-substituted-1-[5-methyl-1-(2-pyrimidinyl)-4-pyrazolyl]-1-trans-propenes in order to improve the in vitro and in vivo activity of our prototype 3-[4-(3-chlorophenyl)-1-piperazinyl]-1-[5-methyl-1-(2-pyrimidinyl)-4-pyrazolyl]-1-trans-propene (2) were synthesized and evaluated by assays of growth inhibition against several tumor cell lines in vitro and antitumor activity against some tumor models when dosed both intraperitoneally and orally in vivo. Compounds 7a and 7e, the 3,5-difluorophenyl and 3,5-dichlorophenyl analogues of 2, respectively, showed significantly more potent cytotoxicity than 2 in vitro and potent antitumor activities without causing decrease of body temperature related to side effects.     

High‐viscosity polyesters from secondary alicyclic 1,4‐cyclohexanedicarboxylic acids and hydroquinones with thionyl chloride/pyridine condensing agent

High‐viscosity polyesters can be prepared by the polycondensation of secondary aliphatic trans‐cyclohexanedicarboxylic acid (t‐CHDC) and hydroquinones using SOCl₂/pyridine condensing agent at 80°C. Incorporation of its cis‐isomer significantly affected η_inh and the thermal property of the resulting copolymers. The copolymers of t‐CHDC, hydroquinones, and p‐hydroxybenzoic acid having different monomer sequences were prepared by changing the order of introduction of monomers.     

Effects of crown ether on hydrogenation over nickel and cobalt boride catalysts: effects in catalyst preparation and effects as additives

The nickel and cobalt boride catalysts prepared in the presence of crown ethers show different selectivities from the ordinary boride catalysts in the reduction of cycloalkene, styrene oxide, and 4-t-butylcyclohexanone.     

Mössbauer spectroscopic study on chemical changes of iron compounds with the aid of sulfate-reducing bacteria

⁵⁷Fe Mössbauer spectra were measured of reaction products formed during an incubation experiment with sulfate-reducing bacteria, which were isolated from estuarine sediments of the Tama River in Tokyo. The spectrum of the product incubated for several days showed some overlapping sextets. This product had a different chemical form from amorphous iron monosulfide produced by inorganic reaction between ferrous and sulfide ions. It was estimated that the structure of nearest neighbor of iron in this product was similar to that of pyrrhotite (Fe_1?x S). After several months of incubation, other singlet and doublet appeared successively on the spectrum, corresponding to mackinawite (FeS_1?x ) and new sulfide, respectively. Both values of isomer shift and quadrupole splitting of new sulfide increased with increasing incubation time and approached those of pyrite (FeS₂). Extended X-ray absorption fine structure (EXAFS) showed that iron atoms were coordinated by sulfur in the incubation product.     

Photoviscoelastic analysis of thermal stress in a quenched epoxy beam

This paper reports on a procedure for photoviscoelastic analysis where the axes of principal stress, principal strain and polarization of light coincide in the presence of a large temperature change. More specially, the transient-thermal stress and strain due to stress in an epoxy beam subjected to quenching from both the upper and lower surfaces, are determined using the time-temperature-equivalent law for stress, strain and birefringence. The transient-thermal stress and strain in the beam were determined experimentally using hereditary integrations from the measurement of the transient temperature and birefringence due to the quenching of the beam. The transient thermal stress and strain were also calculated theoretically using the linear-viscoelastic theory. The experimentally determined thermal stress agrees closely with the theoretical results. The experimentally determined strain agrees qualitatively with the theoretical values. Thus, it is concluded that the photoviscoelastic technique is useful in analyzing the proposed problem.Paper was presented at 1982 SESA/JSME Spring Meeting held in Maui and Oahu, HI on May 23–28, 1982.