Synthesis of novel 1,4-, 3,4-, and 4,5-dihydropyrimidines: First successful POCl3 chlorination and regioselective alkoxycarbonylation

Chlorination of 5,6-dihydropyrimidine-4-(3H)-one derivatives (1) with POCl₃ gave 1,4(3,4)-dihydropyrimidines (3), whose alkoxycarbonylation (ClCOOREt₃N or NaH) afforded regioselectively novel compounds (4). A new Pummerer rearrangement of compound (1, X= ---S(O)CH₃) with ₃, gave compound (5h).     

Preparation and photochromic properties of oligomeric poly(dimethylsiloxane) with the spiropyran or spirooxazine moiety in the side chain

Spirobenzopyran 1 , with the 3-(diethoxymethylsilyl)-propyl group at the N atom, was synthesized. The condensation reaction of the spiropyran 1 and diethoxydimethylsilane gave oligomeric poly(dimethylsiloxane) with the spiropyran moiety in the side chain. The oligomer was photochromic; its colour changed from colorless to purple-red on uv irradiation and the color faded on visible irradiation or on standing in the dark. The half-decay time of the thermal decoloration was about twice that of monomeric spiropyran dissolved in the dimethylsiloxane oligomer. Photochromic poly(dimethylsiloxane) with the spirooxazine moiety in the side chain was also prepared.     

Synthesis and central nervous system stimulant activity of camphor-1,2,4-benzotriazines fused with five and six-membered heterocycles

Novel camphor-1,2,4-triazines fused with imidazole 2–3 , thiadiazole 4 , 1,2,4-triazole 7 , pyrimidine 9–13 and 1,3,5-triazine 14 , were synthesized starting from (5R,8S)-3-amino-5,9,9-trimethyl-5,6,7,8-tetrahydro-5,8-methano-1,2,4-benzotriazine 1 . Evaluation of central nervous system stimulant activity demonstrated that the presence of a N-N group at C-3 position of 1,2,4-benzotriazine will be essential for the activity.     

Development of miniaturized multi-channel high-performance liquid chromatography for high-throughput analysis

We have developed miniaturized multi-channel high-performance liquid chromatography (HPLC) system. With this system, we can simultaneously separate multiple samples, using a single high-pressure gradient pump, a chip-based sample injection unit, a monolithic silica capillary column array, and a multi-channel UV detection unit based on fiber optics. The injection unit has a simplified structure composed of brass housing and a quartz microchip having microchannels and access ports, which enable a direct injection of sample to multi-channel by commercial multichannel micropipette. Moreover, that possesses a function of microvalve, and on-chip definition of sample injection plugs achieved with a cross channel injection method, providing each column of monolithic silica capillary array. The substances in channels were simultaneously detected with UV having multiple cells. Standard samples were analyzed for characterizing newly developed system, and sharp peaks were obtained with reproducibility data of < 0.9% (R.S.D.). Analysis of tryptic digestion of casein was also employed. These results show that the novel multi-channel HPLC system has the benefits for the high-throughput analysis in the post-genomic analysis/combinatorial chemistry.     

Distribution and dynamics of radionuclides and stable elements in the coastal waters off Rokkasho Village, Japan, prior to the opening of a nuclear reprocessing facility

A nuclear fuel reprocessing facility is currently under construction in Rokkasho Village, Aomori, Japan. After completion and start-up, this facility will discharge radionuclides into the Pacific Ocean through an outlet pipe set on the seafloor offshore. For future assessments of the stability of these radionuclides in the environment, a sufficient understanding of the behavior of radionuclides in this ocean ecosystem before the start-up of the facility is necessary. To understand the processes by which radionuclides and various other types of elements are eliminated from seawater, we measured the sedimentation flux of suspended particles in the coastal waters off Rokkasho Village where the sea emissions pipes will be placed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis of poly (ether-sulfone-amide)s by palladium-catalyzed polycondensation of aromatic dibromides containing ether sulfone structure,aromatic diamines,and carbon monoxide

A general method for the preparation of aromatic poly (ether-sulfone-amide)s has been developed. Polymerization is based on the palladium-catalyzed polycondensation of aromatic dibromides containing ether sulfone structural units, aromatic diamines, and carbon monoxide. Reactions were carried out in N, N-dimethylacetamide (DMAc) in the presence of palladium catalyst, triphenylphosphine, and 1,8-diazabicyclo [5,4,0]–7–undecene (DBU), and gave a series of poly (ether-sulfone-amide)s with inherent viscosities up to 0.86 dL/g under mild conditions. The polymers were quite soluble in strong acids, dipolar aprotic solvents, and pyridine. Thermogravimetry of the polymers showed excellent thermal stability, indicating that 10% weight losses of the polymers were observed in the range above 470°C in air. The glass transition temperatures of the polymers were around 230°C, which are higher than those of poly (ether-sulfone) analogues. These polymers also showed the good tensile strengths and tensile modulus. © 1994 John Wiley & Sons, Inc.