Evaluation of mass transfer rate during Ziegler-Natta propylene polymerization

Mass transfer which affects the rate of propylene polymerization with titanium trichloride–triethylaluminum, has been evaluated by use of a new method developed for this heterogeneous reaction. The polymerization was carried out with the usual flask reactor equipped with a paddle stirrer; the rate of gas absorption into the polymerization slurry was proportional to stirring speed and the reciprocal of the total amount of polymers produced. It has been confirmed that the polymerization rate separated from the absorption rate is purely kinetic (propagation), and an effective physical process, such as monomer transfer through a polymer film covering the catalyst surface, no longer exists.     

Novel ring transformation reactions of xanthine derivatives

The novel ring transformation reactions were found in the reactions of 1,3,7,9-tetra-alkyl-8,9-dihydroxanthines and acetylenic compounds. The reaction of the dihydroxanthine with DMAD gave a propellane type compound and with methyl propiolate afforded the similar type compound and a pyrimido[4,5-b]diazepine derivative. The mechanism of these reactions was also discussed.     

Marine sterols—IV : Structure and synthesis of amuresterol,a new marine sterol with unprecedented side chain,from Asterias amurensis lütken

Amuresterol, a new marine C₂₇ sterol, was isolated from an asteroid Asterias amurensis, and its structure was confirmed as biogenetically unprecedented 22-trans-27-nor-(24S)-24-methylcholesta-7, 22-dien-3β-ol (1) from the spectral data and by synthesis. Gas-liquid chromatography indicated that 1 is a common sterol in six species of asteroids collected in Hokkaido.     

Synthetic studies on macrolactin A by using a (diene)Fe(CO)3 complex

The stereoselective synthesis of the two segments 3 and 4 of macrolactin A 1 is described. Macrolactin A is a 24-membered polyene macrolide antibiotic, which is of interest due to a strong activity against B16-F10 murine tumor cell and HIV-1 virus. The key step of the synthesis is the 1,2-migration reaction of a (diene)Fe(CO)₃ complex with a introduction of the thiol group to construct the unstable (E,Z)-conjugated dienic moiety (C8-C11).     

Study on tumor affinity of technetium-99m-labeled radiopharmaceuticals. (2) 99mTc-Sn-diphosphonate (99mTc-EHDP), 99mTc-Sn-dimercaptosuccinic acid (99mTc-DMSA), and 99mTc-Sn-diethyl stilbestrol diphosphate (99mTc-DSDP)]

The authors have examined the tumor affinity of various 99mTc-labelled radiopharmaceuticals to Ehrlich's tumor for the purpose of delineating positively human malignant neoplasm. This paper includes biologic distributions of 99mTc-Sn-diphosphonate (99mTc-EHDP), 99mTc-Sn-dimercaptosuccinic acid (99mTc-DMSA) and 99mTc-Sn-diethyl stilbestrol diphosphate (99mTc-DSDP, 99mTc-Honvan) as the second report on the tumor affinity to the Ehrlich-bearing mice. (a) Tumor concentration of 99mTc-EHDP was lowest and the positive delineation of implanted tumor with 99mTc-EHDP was poorest in sequential images, though the active accumulation to some soft tissue maglinant neoplasms, the breast cancer and the thyroid cancer, has been reported. (b) Tumor concentration and tumor to blood ratio of 99mTc-DMSA were not so high on the contrary of our expectation that 197Hg-DMSA may show the high tumor concentration and the high tumor to blood ratio like 197Hg chlormerodrin as same renal scanning radiopharmaceuticals. (c) Tumor concentration of 99mTc-DSDP was highest. Tumor to blood concentration ratio, however, was lower than that of the above mentioned radiopharmaceuticals but tumor to liver ratio and/or tumor to lung ratio was over 1.0 at the earlier time. Biologic distribution of 99mTc-DSDP was similar to that of 32P labeled DSDP and then it is presumed that 99mTc is labeled at phosphate ester of DSDP which is dephospholytated immediately by phospholylase in vivo following the intravenous injection. Therefore, it may be assumed that the accumulation mechanism of 99mTc-DSDP to Ehrlich's tumor is related to the phospholylase activity in neoplasms but is not known precisely.     

Second harmonic generation in inclusion complexes

Second harmonic generation (S.H.G.) in inclusion complexes between dimethyl -cyclodextrin (dimethyl -CD) and nitroaniline derivatives occurs. This is due to the destruction of the centrosymmtric crystal structure in nitroaniline derivatives caused by forming inclusion complexes. S.H.G. intensity of dimethyl -CD complex with N-methyl-nitroaniline is 5.5 times as large as that of urea.