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| 1.
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Somei, Masanori ; Yamada, Fumio ; Yamazaki, Yoshihisa ; Shinkura, Akiko
概要:
We developed a novel synthesis of 2-aminoindan derivatives, having a 2-methyl-1-propenyl group at the 1-position and oxygen functional groups in the benzene ring, in 8 or 9 steps from vanillin.
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| 2.
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Murata, Yasue ; Kinoshita, Hideki ; Inomata, Katsuhiko
概要:
The syntheses of 3,4-disubstituted 2-tosylpyrroles and 5-tosyl-1,5-dihydro-2H-pyrrol-2-ones were accomplished via 3,4-disubstituted 2-iodo-5-tosylpyrroles starting from ethyl 3,4-disubstituted 2-pyrrolecarboxylates.
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| 3.
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Somei, Masanori ; Hayashi, Hiroyuki ; Ohmoto, Shinobu
概要:
金沢大学大学院自然科学研究科生理活性物質科学<br />金沢大学薬学部<br />Indigo was converted to 2,2′-bisindole by the direct reduction with zinc in ace
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tic acid and acetic anhydride under argon or hydrogen atmosphere. Reduction with tin and iron afforded 3-acetoxy-2,2′-bisindole predominantly. Useful building blocks such as 1-acetyl-2,3-dihydro-, 3-acetoxy-3′-acetyl-, and 3-acetoxy-1,3′-diacetyl-2,2′-bisindoles were also produced depending on metal and reaction conditions.
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| 4.
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Suzuki, Masatatsu ; Sugisawa, Toshiharu ; Uehara, Akira
概要:
Two dinuclear cobalt(II,II) complexes, [Co2(tpdp)(CH3COO)](ClO4)2·0.5H2O (1) and [Co2(tmdp)(CH3COO)](ClO4)2·H2O (2), wer
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e prepared, where Htpdp and Htmdp are 1,3-bis[bis(2-pyridylmethyl)amino]-2-propanol and 1,5-bis[bis(2-pyridylmethyl)amino]-3-pentanol respectively. Their electronic spectral and magnetic data revealed that 1 and 2 are five-coordinate in the high-spin state, in the same manner as [Co2(bpmp)(CH3COO)]2+ (3) (Hbpmp=2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol). The complexes reacted with molecular oxygen to form μ-peroxo complexes in dichloromethane and acetonitrile. The oxygen affinity of the complexes decreased in the order of 3>2>1. The relationships between the oxygen affinities and (1) the donor abilities of dinucleating ligands, (2) the energies of the charge-transfer bands (O22− to Co3+) of the μ-peroxo complexes, and (3) the redox potentials of the Co3+–O2−–Co3+/Co3+–O22−–Co3+ couple indicated that a steric effect arising from the dinucleating ligands contributes significantly to the oxygen affinities of the complexes.
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| 5.
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Ikeda, Masazumi ; Ohtani, Shinji ; Okada, Michiyo ; Minakuchi, Emi ; Sato, Tatsunori ; Ishibashi, Hiroyuki
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| 6.
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Somei, Masanori ; Kodama, Atsushi
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金沢大学大学院自然科学研究科生理活性物質科学<br />金沢大学薬学部
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| 7.
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Tsutiya, Ryokichi
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| 8.
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Tsutiya, Ryokichi
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| 9.
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Sumiyoshi, T. ; Kido, H. ; Sakamoto, H. ; Urasaki, K. ; Suzuki, K. ; Yamaguchi, N. ; Mori, Hirofumi ; Shiba, Kazuhiro ; Yokogawa, K. ; 柴, 和弘
概要:
金沢大学疾患モデル総合研究センター<br />An in vivo receptor binding technique was applied to evaluate the affinities of risperidone and h
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aloperidol for dopamine-D2 receptors (D2) and serotonin-5-HT2 receptors (5-HT2) in rat brain with [3H]YM-09151-2 and [3H]ketanserin as selective ligands. Radioactivities were obtained in the striatum, frontal cortex, and cerebellum of the rats treated with the ligands. Time course study of receptor occupancy at 25 to 250 min after single doses of the drugs (1 mg/kg, IP) showed higher 5-HT2 occupancy in the frontal cortex and lower D2 occupancy in the striatum by risperidone than by haloperidol. Dose-response analysis of receptor occupancy revealed risperidone demonstrated higher binding affinity for 5-HT2 than for D2, while the reverse was observed with haloperidol. It appeared that risperidone (1 mg/kg, IP), but not haloperidol (1 mg/kg, IP), demonstrated regional selectivity in D2 occupancy favouring frontal cortex more than the striatum. That risperidone displayed a higher ratio of 5-HT2 to D2 in occupancy than haloperidol is in agreement with the previous findings obtained in vitro. © 1994.
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| 10.
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Sugimoto, Hideki ; Nagayama, Toshihiko ; Maruyama, Sachihito ; Fujinami, Shuhei ; Yasuda, Yuichi ; Suzuki, Masatatsu ; Uehara, Akira
概要:
A new dinucleating ligand containing a sterically bulky imidazolyl group, Ph-Htidp (N,N,N′,N′-tetrakis[(1-methyl-4,5-dip
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henyl-2-imidazolyl)methyl]-1,3-diamino-2-propanol), and its μ-alkoxo-diiron(II) complexes [Fe2(Ph-tidp)(RCO2)](ClO4)2, (RCO2 = C6H5CO2 (1), C6F5CO2 (2), CF3CO2 (3), and C2H5CO2 (4)), were synthesized. The structure of complex 1 was determined by X-ray crystallography. Complex 1 crystallizes in the monoclinic space group P21/c with a = 13.464(2), b = 19.223(4), c = 31.358(4) Å, β = 92.84(2)°, and Z = 4. The complex has a doubly-bridged structure with μ-alkoxo of Ph-tidp and μ-benzoate; the two iron centers have a distorted five-coordinate structure with N3O2 donor set. All the complexes showed fairly good reversible oxygenation below −30 °C in CH2Cl2, which was monitored by UV-vis and NMR spectroscopies, and dioxygen up-take measurements. Introduction of 4,5-diphenyl substituents into 2-imidazolyl group stabilized the μ-peroxo diiron species against irreversible oxidation, just as introduction of 6-methyl substituent into 2-pyridyl group did. Phenyl substituents appear to weaken the electron donor ability of a dinucleating ligand to stabilize divalent oxidation state of iron and to form a hydrophobic cavity for a O2 binding site, which would suppress the irreversible oxidation and facilitate the reversible oxygenation. Dioxygen affinities of the Ph-tidp and Me4-tpdp diiron(II), and the tpdp and bpmp dicobalt(II) complexes were measured, [Fe2(Me4-tpdp)(RCO2)]2+ (RCO2 = C6H5CO2 and RCO2 = CF3CO2) and [Co2(L)(RCO2)]2+ (L = tpdp, RCO2 = CH3CO2, and L = bpmp, RCO2 = C6F5CO2, and CF3CO2), where Me4-tpdp, tpdp, and bpmp are N,N,N′,N′-tetrakis[(6-methyl-2-pyridyl)methyl]-1,3-diamino-2-propanolate, N,N,N′,N′-tetrakis(2-pyridylmethyl)-1,3-diamino-2-propanolate, and 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenolate, respectively. Within a series of the Ph-tidp diiron(II) complexes, dioxygen affinity is well correlated with electron donor ability of bridging carboxylates (1 (C6H5CO2) > 2 (C6F5CO2) > 3 (CF3CO2)). In contrast to the above trend, dioxygen affinities of the Ph-tidp complexes are lower than those of the Me4-tpdp complexes, although electron donor abilities of the Me4-tpdp complexes are weaker than those of the Ph-tidp complexes. Significant enhancement of dioxygen affinity was observed for both iron and cobalt complexes with 2,6-bis(aminomethyl)phenolate bridging skeleton compared to the complexes with a 1,3-diamino-2-propanolate bridging one. Thermodynamic study suggested that the observed enhancement is mainly attributable to a favorable entropy effect along with a steric effect.
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