A novel and efficient synthesis of porphine

meso-Tetra(n-hexyloxycarbonyl)porphyrin was found to be converted into porphine, the mother compound of porphyrins, in a 77% yield when heated in aqueous sulfuric acid at 180 °C over 30 min under an inert atmosphere. The observation demonstrates that the substituted porphyrin serves as a novel and useful precursor for porphine.     

Structure of Sol-Gel-Derived Sodium Dititanate Glass

The sodium dititanate, Na₂O·2TiO₂ glass was prepared by the sol-gel method. The structure of the glass, especially local environment of Ti⁴⁺ ions was examined using X-ray diffraction and X-ray absorption fine structure (XAFS) analyses, and was compared with that of the melt-derived glass with the same composition. It was found that Ti⁴⁺ ions are rather in five-fold coordination state, forming TiO₅ pyramids with one doubly bonded Ti=O in the gel-glass, while they were in lower coordination state or four-fold coordination in the melt-derived glass.     

Excited states of porphyrin isomers and porphycene derivatives: a SAC-CI study

Excited states of free-base porphyrin isomers, porphycene (Pc), corrphycene (Cor), and hemiporphycene (hPc), were studied by the Symmetry-Adapted Cluster (SAC)/SAC-Configuration Interaction (CI) method. The absorption peaks of the porphyrin isomers were assigned on the basis of the SAC-CI spectra. The X, Y, X', and Y' bands of the porphyrin isomers, which have weak intensities, are identified. The differences in the Q-band absorptions among the isomers were clearly explained by the four-orbital model. In Cor and hPc, the wave function of the B-band corresponds to the mixture of the four-orbital excitations and the optically forbidden excitation of free-base porphin (P), due to the molecular symmetry lowering in the isomers. The B-band character is described by the five-orbital model in Pc and the six-orbital model in Cor and hPc. Two tetrazaporphycenes and two ring-extended (dibenzo) porphycenes were designed, and the Q-band transition moment was successfully controlled. These examples show that the control of the four-orbital energy levels is the guiding principle for pigment design in porphyrin compounds.     

Hyperfine interactions in icosahedral quasicrystals: a Mössbauer study

Icosahedral Al₆₅Cu₂₀Fe₁₅ and Al₄₀Cu_9.9Ge₂₅Mn₂₅ ⁵⁷Fe_0.1 quasicrystals are studied using⁵⁷Fe transmission Mössbauer experiments. The spectra are analyzed by distributions of electric-quadrupole interaction accounting for line asymmetries. Temperature dependences of the hyperfine parameters derived comprising average values ofP() distributions, corresponding standard deviations and center shifts are presented in a whole range from 8 to 300 K.     

Local order of icosahedral quasicrystals studied by Mössbauer spectroscopy

Thermodynamically stable Al-Cu-Fe and Fe-doped ferromagnetic Al-Cu-Ge-Mn icosahedral quasicrystals are studied by⁵⁷Fe transmission Mössbauer spectroscopy and X-ray diffraction experiments. Al₆₅Cu₂₀Fe₁₅ quasicrystalline alloy was subjected to a mechanical grinding (MG) for up to 800 hours in a ball mill. Presence of the amorphous phase which co-exists with the quasicrystalline one is revealed in the early stage of MG. Mössbauer measurements were performed on icosahedral Al₄₀Cu_10–x Ge₂₅Mn₂₅Fe _x quasicrystal (x0.1; 3) in a temperature range from 10 K to 548 K. It was found that a magnetic transition occurs at about 30 K which is far belowT _c reported in the literature. It is concluded that AlGeMn ferromagnet which is present in the samples does not affect the magnetic transition observed and the transition is an intrinsic property of the Al-Cu-Ge-Mn host alloy.Samples of icosahedral quasicrystals were kindly provided by Profs. A. Inoue, T. Masumoto and P. H. Shingu. Ball milling was performed in Kyoto University by a courtesy of Prof. P. H. Shingu. This work was supported by the project for priority areas on properties of quasicrystals (No. 01630003) from the Japanese Ministry of Education, Science and Culture.     

Melting behavior of highly stretched isotactic polypropylene film

Isotactic polypropylene film was stretched in poly(ethylene glycol) at 140°C and its melting behavior was investigated by using a differential scanning calorimeter (DSC-1B). The shape of the melting curve depends largely on the stretching ratio, v. A sample stretched to moderate extension (1 < v < 3.5–4) has only a single melting peak (163°C) in the thermogram. When the sample is stretched beyond v = 3.5–4, the thermogram becomes more and more complex with increase of v, and some peaks appear when stretched to 10 < v < 13. The lowest peak which is considered to be the melting peak of the intermolecular crystals produced by the unfolding of chain molecules in the lamellae develops gradually with increase of v. In the thermogram for v = 18 the lowest temperature peak is most pronounced, in contrast to the highest temperature peak which decreases markedly in intensity. The phenomenon shows that large amounts of lamellar crystals are converted to intermolecular crystals in this region. On further stretching (v > 20) a very sharp high temperature peak appears, whose half-width is about 1°C. Qualitatively similar results were obtained for the samples stretched in poly(ethylene glycol) at 150°C and in air at 140 and 150°C.     

Studies on the synthesis of compounds related to adenosine 3',5'-cyclic phosphate. IX. Synthesis and cytotoxic effect of adenosine 3',5'-cyclic alkylphosphoramidates.

A series of adenosine 3',5'-cyclic monophosphoramidates (3, cAMP amidates), including long-chain alkyl amidates, were synthesized from adenosine 3',5'-cyclic monophosphate (1, cAMP) by means of a one-pot reaction. This reaction proceeded by the treatment of cAMP tributylammonium salt (2) with phosphorus pentachloride (PCl5) and alkylamine in N,N-dimethylformamide (DMF). Compounds 3 synthesized were investigated to determine their cytotoxic activities on the growth of mouse mastocytoma P-815 cells, mouse mammary tumor FM3A cells, and human mammary tumor ZR-75 cells in culture. It was found that compounds 3h-m showed significant cytotoxic activities against these cell lines, and that cAMP decylamidate (3j) was the most cytotoxic compound (the concentration required for 50% inhibition of cell growth, ID50 = 6.0, 15.0, 2.2 microM, respectively); the antitumor effect on P-815 cells by a total packed cell volume method showed 81.8% inhibition. The cytotoxic activity of 3 increased with the increase in alkyl chain length up to 10 carbon atoms and decreased in compounds having longer alkyl chain.     

Studies on the biaxial stretching of polypropylene film. III. Electron microscopic observation of the one-step biaxial stretching of isotactic polypropylene spherulites

Polypropylene films of various isotacticities and crystallinities were stretched biaxially in one step in air at 140–152°C or polyaxially in poly(ethylene glycol) at 130–160°C, and the morphological changes were studied by electron microscopy (replica). In the initial stage of stretching, with v_A = 1.4, the spherulites of one of the films used for the experiment were broken both from the centers and boundaries, and those of another film were broken mainly from the center. This difference in the deformation behavior seems to be characteristic of the film properties and independent of the method of stretching, although the factors involved are still unknown. On further stretching (v_A = 22), well annealed spherulites were broken into many small blocklike fragments with unfolded fibrils running among them, particularly at the low stretching temperature (140°C), and fibrillation proceeded at the expense of the residual fragments. In the case of quenched or slightly crystallized material, the fragments were dendritic and divided into finer and finer fibrils on stretching. At elevated temperature, however, even for well annealed spherulites, the deformation behavior resembles that of the quenched material, and at a high degree of stretching the spherulites take on the fibrillar net structure in every case. In films containing a high amount of atactic fraction, radial, tangential, and boundary cracking occurred more easily, and broad fibrils were observed across the cracks.     

Ring transformation of 6H-cyclopropa[e]pyrazolo[1,5-a]pyrimidine. IV (1). Reduction and reaction of 5a-acetyl-6a-ethoxycarbonyl-5a,6a-dihydro-6H-cyclopropa[e]pyrazolo[1,5-a]pyrimidine-3-carbonitriles with primary amines

The reaction of 5a-acetyl-6-ethoxycarbonyl-5a,6a-dihydro-6H-cyclopropa[e]pyrazolo[1,5-a]pyrimidine-3-carbonitrile ( 1a ) with benzylamine gave ethyl l-benzyl-5-cyano-8a,9-dihydro-2-methyl-1H-pyrrolo[3,4-e]-pyrazolo[1,5-a]pyrimidine-8a-carboxylate ( 2a ), in addition to 5-acetyl-3-benzylamino-1-(4-cyanopyrazol-3-yl)- 2-pyridone ( 3 ). Reaction of 1a with aniline gave ethyl 6-acetyl-8-anilino-3-cyano-7,8-dihydro-4H-pyrazolo-[1,5-a][1,3]diazepine-8-carboxylate ( 4 ), in addition to ethyl 3-cyano-7-methyl-6-pyrazolo[1,5-a]pyrimidine-acrylate ( 5 ). On the other hand, the same reactions of 1b with benzylamine or aniline gave 2b or 8b , respectively. Though catalytic hydrogenation of 1a over 5% palladium-carbon proceeded by ring fission of cyclopropane ring to give 9 , 1a (or 1b ) afforded 4,5-dihydro derivatives ( 13 or 15 ) by catalytic hydrogenation over platinum oxide. The reactivity of 5-methoxy-4,5,5a,6a-tetrahydro-6H-cyclopropa[e]pyrazolo[1,5-a]pyrimidine ( 16 ), which are related analogs of 1a,b , is also described.