-
Godwin C. EBI, Keith R. BRAIN, Oleka K. UDEALA
1996 Volume 44 Issue 4 Pages
639-641
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
1-n-Butyl-3-p-tosylurea (tolbutamide) does not incorporate the secondary amines, piperidine, diethylamine, dimethylamine, dipropylamine, pyrrolidine and morpholine, to any significant extent in its normal Mannich reaction under alkaline conditions in refluxing methanol, accetonitrile and dioxane. Instead 3-n-butyl-2-oxo-1, 5-di-p-tosyl-perhydro-1, 3, 5-triazine and 3, 5-di-n-butyl-2-oxo-1-p-tosyl-perhydro-1, 3, 5-triazine are mainly formed usually in good yields. These triazines have been isolated and characterized, and a mechanism is proposed for their formation.
View full abstract
-
Koji HASHIMOTO, Yoshihiko OKAICHI, Daisuke NOMI, Hisashi MIYAMOTO, Mas ...
1996 Volume 44 Issue 4 Pages
642-645
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
(S)-(-)-Nadifloxacin [(S)-(-)-9-fluoro-6, 7-dihydro-8-(4-hydroxy-1-piperidyl)-5-methyl-1-oxo-1H, 5H-benzo[i, j]quinolizine-2-carboxylic acid, (S)-(-)-OPC-7251], an antibacterial agent, was synthesized from (S)-(-)-5, 6-difluoro-2-methyl-1, 2, 3, 4-tetrahydroquinoline (DFTQ), which was prepared by the optical resolution of recemic DFTQ with 2, 3-di-O-benzoxyl-L-tartaric acid. Racemization of the undesired enantiomer [(R)-(+)-DFTQ] was studied in the presence of various acids and the best result was obtained in the case of methanesulfonic acid. The absolute configuration of (-)-nadifloxacin was determined as S by X-ray crystallographic analysis.
View full abstract
-
Takeshi KOIKE, Katsuya YAMAZAKI, Naoko FUKUMOTO, Kayoko YASHIRO, Naoki ...
1996 Volume 44 Issue 4 Pages
646-652
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Dictamnol (1), a trinor-guaiane type seequiterpene from the roots of Dictamnus dasycarpus TURCZ., was synthesized from 4α-acetoxy-3, 4, 4a, 5, 6, 8aβ-hexahydro-4aα-methyl-2H, 8H-naphthalene-1, 7-dione (3) by the utilization of an intramolecular base-induced rearrangement with sodium tert-amylate as a key step (27→28). Compound 3 was prepared from a chiral dione, (S)3, 4, 8, 8a-tetrahydro-8aα-methyl-2H, 7H-naphthalene-1, 6-dione (2) according to the procedure of de Groot et al. [J. Org. Chem., 48, 4380 (1983)] and was transformed into dictamnol (1) via 22, 23, 24, 26, 27, 28, and 30. Thus, the absolute configuration of dictamnol is as represented by formula 1.
View full abstract
-
Yoshinori TOMINAGA, Satoshi TAKADA, Shinya KOHRA
1996 Volume 44 Issue 4 Pages
653-660
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
2-[(Trimethylsilylmethylamino)(methylthio)]methylene- and 2-[(trimethylsilylmethylthio)(methylthio)]methylene-1, 3-indandiones (1a, b), which are readily prepared by reaction of the corresponding 2-bis(methylthio)methylene-1, 3-indandione (12) with trimethylsilylmethylamine (13a) and trimethylsilylmethylmercaptan (13b), were found to be synthetic equivalents of carbonyl alkylidene-azomethine and alkylidene-thiocarbonyl ylides. Reaction of 1a, b with reactive hetero-dipolarophiles such as aldehydes and ketones and reactive alkenes in the presence of cesium fluoride gave 1, 3-dipolar cycloadducts, 4, 5-dihydro-2-(1, 3-dioxoindan-2-ylidene)-1, 3-oxazoles (6a-f, 7a-c), 4, 5-dihydro-2-(1, 3-dioxoindan-2-ylidene)pyrroles (8a-c), 2-alkylidene-1, 3-oxathiolanes (9a-k, 10a, b), and 2-alkylidenethiophenes (11a-c), via formation of the counterpart of the carbonyl-substituted intermediate with concomitant desilylation.
View full abstract
-
Salwa F. FARAG, Nasr A. EL-EMARY, Masatake NIWA
1996 Volume 44 Issue 4 Pages
661-664
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Five cis- and trans-eudesmanolide sesquiterpenes were isolated from Wedelia prostrata (Compositae) collected in Egypt and their structures were elucidated by spectroscopic methods. The conformations of the trans-eudesmano-lides are discussed on the basis of their coupling constants in the
1H-NMR spectra.
View full abstract
-
Nobuko SHIMIZU, Hiroyuki AKITA, Takeshi KAWAMATA
1996 Volume 44 Issue 4 Pages
665-669
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
The enzymatic esterification or hydrolysis of 1-hydroxy((±)-1), 1-acetoxy((±)-2) and 1-butyryloxy-5-methyl-3-vinylcyclohex-2-ene ((±)-3) was carried out using lipid-lipase aggrgates. The esterification of (±)-1 provided (1S, 5S)-1 with >99% ee using lipid-lipase "Amano P" with vinyl butyrate as the acylating reagent.
View full abstract
-
Yoshie HORIGUCHI, Takehiro SANO, Yoshisuke TSUDA
1996 Volume 44 Issue 4 Pages
670-674
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Thermal cycloaddition of 4-benzoyl-5-ethoxycarbonyl-1-phenyl-1H-Pyrrole-2, 3-dione (dioxopyrroline) 1 to electron-rich olefins smoothly proceeded in a highly regio- and stereoselective manner to give pyranopyrrole derivatives in excellent yields. The reaction is a typical inverse-electron-demand hetero Diels-Alder reaction, in which dioxopyrroline behaves as an electron-deficient diene.
View full abstract
-
Shinji NAGUMO, Shigeyuki IRIE, Hiroyuki AKITA
1996 Volume 44 Issue 4 Pages
675-680
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
The reaction of methyl 4, 5-epoxy-(2E)-pentenoate (1) with various arylcopper reagents was studied. Basically, all arylcopper reagents react with 1 in SN2 fashion. However, addition of BF
3 causes reversal of the regioselectivity, which can be rationalized in terms of a two-step conversion by way of methyl 4-bromo-5-hydroxy-2-pentenoate (5).
View full abstract
-
Yoshie HORIGUCHI, Takehiro SANO, Fumiyuki KIUCHI, Yoshisuke TSUDA
1996 Volume 44 Issue 4 Pages
681-689
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Thermal cycloaddition reaction of 4-benzoyl-5-ethoxycarbonyl-1H-pyrrole-2, 3-dione (dioxopyrroline) 1 with 1, 3-dienes caused two types of Diels-Alder (D-A) reaction in a competitive manner. One is the hetero D-A reaction in whch dioxopyrroline acts as an electron-deficient diene and the 1, 3-diene acts as an electron-rich dienophile. The other is the normal D-A reaction in which diosopyrroline acts as an electron-deficient dienophile. The 1, 3-dienes bearing electron-rich substituents undergo the D-A reaction via the normal pathway, while the 1, 3-dienes which do not bear an electron-donating group predominantly undergo the hetero D-A reaction. When the normal D-A pathway is sterically hindered, the hetero D-A pathway occurs exclusively.
View full abstract
-
Rumiko KAMAYA, Kazuo MASUDA, Kiyomi SUZUKI, Hiroyuki AGETA, Hong-Yen H ...
1996 Volume 44 Issue 4 Pages
690-694
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Four sesterterpenoids, cheilanthenetriol (1) and three new compounds, were isolated from the fronds of aleuritopteris mexicana together with the triterpenoids squalene, tirucalla-7, 21-diene, neohop-12-ene, neohop-13(18)-ene, fern-7-ene, fern-8-ene, ferna-7, 9(11)-diene, adian -5-ene and adian-5-ene ozonide, and the flavonoids 3, 5-dihydroxy-7, 4'-dimethoxyflavone and 5-hydroxy-7, 47-dimethoxyflavone. The structures of the three new compounds were established as (17Z)-13, 19-epoxycheilanth-17-en-6α-01 (2), 18-episcalar-16-ene-6α, 19-diol (3) and 16α, 19-epidioxy-18-episcalar-17(25)-en-6α-ol (4) on the basis of detailed spectral analyses.
View full abstract
-
Rumiko KAMAYA, Kazuo MASUDA, Hiroyuki AGETA, Hsien-Chang CHANG
1996 Volume 44 Issue 4 Pages
695-698
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Five new sesterterpenoids were isolated from the frounds of Aleuritopteris agetae, together with the triterpenoids squalene, tirucalla-7, 21-diene and hop-21-ene, and the flavonoids 3, 5-dihydroxy-7, 4'-dimethoxyflavone and 5-hydroxy-7, 4'-dimethoxyflavone. The structures of five new compounds were determined to be (17Z)-cheilantha-13(24), 170diene-6α, 19-diol (1), (17Z)-cheliantha-13(24), 17-diene 1β, 6α, 19-triol (2), (17Z)-19-acetoxycheilantha-13(24), 17-diene-1β, 6α-diol (39, 17-oxo-18, 19-bisnorchelianth-13(24)-en-6α-ol (4) and 13, 17-dioxo-18, 19, 24-trisnorcheilanth-6α-ol (5) on the basis of detailed spectral analyses.
View full abstract
-
Noriaki KUDO, Misa TANIGUCHI, Kazuo SATO
1996 Volume 44 Issue 4 Pages
699-702
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
An efficient synthetic method for 3-aryl-5-butyl-4-oxazolin-2-ones (6) is described. The reaction of ethyl N-arylcarbamates (10) with 1-bromo-3, 3-dimethyl-2-butanone (9a) or 1-bromo-3-ethyl-3-methyl-2-pentanone (9b) using 2.2 eq of lithium bis(trimethylsilyl)amide afforded 6 in good yields. The reaction mechanisms are discussed.
View full abstract
-
Akemi TOYOTA, Yoshinori ONO, Jun CHIBA, Takumichi SUGIHARA, Chikara KA ...
1996 Volume 44 Issue 4 Pages
703-708
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Direct formation of α-fluorosulfones from sulfoxides bearing α-H atoms merely by reaction with molecular fluorine (5% F
2/N
2) is reported, and a novel non-Pummerer-type mechanism is proposed for this α-fluorination reaction.
View full abstract
-
Haruyuki YOSHIOKA, Yuhji MATSUYA, Tominari CHOSHI, Eiichi SUGINO, Sato ...
1996 Volume 44 Issue 4 Pages
709-714
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
The interferon-α inducer imiquimod (1), possessing an imidazo[4, 5-c]quinoline ring, has been newly synthesized by two routes based on thermal electrocyclic reactions of 1- and 2-azahexatriene systems inovlving the imidazole 4, 5-bond.
View full abstract
-
Manabu NODE, Xiao-jiang HAO, Kiyoharu NISHIDE, Kaoru FUJI
1996 Volume 44 Issue 4 Pages
715-719
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
A total synthesis of (-)-eserethole (2) has been accomplished using the Diels-Alder reaction of (S)-(-)-2-methyl-2-[2-(E)-nitroethenyl]-δ-valerolactone (3) and Danishefsky's diene as a key step. The synthesis of optically pure (-)-eserethole (2) constitutes a formal synthesis of naturaly occurring Calabar bean alkaloids, such as (-)-physostigmine (1), (-)-physovenine (17) and (-)-geneserine (18).
View full abstract
-
Motomasa KOBAYASHI, Taifo MAHMUD, Hisashi TAJIMA, Weiqi WANG, Shunji A ...
1996 Volume 44 Issue 4 Pages
720-724
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Adociacetylenes A (1), B (2), C (3), and D (4) were isolated as new polyacetylenes from an Okinawan marine sponge of Adocia sp. Their chemcial structuers have been elucidated on the bases of their chemcial and physico-chemical properties. Adociacetylenes A (1), B (2), C (3), and D (4) exhibited inhibitory activity in the in vitro endothelial cell-neutrophil leukocyte adhesion assay.
View full abstract
-
Kazumi KONDO, Hidenori OGAWA, Kenji KNAKAYA, Michiaki TOMINAGA, Youich ...
1996 Volume 44 Issue 4 Pages
725-733
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
During our systematic studies on the arginine vasopressin receptor V
1a-antagonistic activity of 1-(1-benzoyl substituted 4-piperidyl)-3, 4-dihydro-2(1H)-quinolinones, we found a general substituent effect on the benzene ring. Hydrogen-bonding ability at the ortho position was especially important for enhancement of the affinity of multi-substituted analogs. Details of the syntheses and structuer-activity relationships for this series are presented.
View full abstract
-
Satoshi YAMAMOTO, Shohei HASHIGUCHI, Shokyo MIKI, Yumiko IGATA, Toshif ...
1996 Volume 44 Issue 4 Pages
734-745
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
A new series of 1, 3-benzoxazine derivatives with a 2-pyridine 1-oxide group at C4 was designed to explore novel K
+ channel openers. Synthesis swas carried out by using a palladium(0)-catalyzed carbon-carbon bond formation reaction of imino-triflates with organozinc reagents and via a new one-pot 1, 3-benzoxazine skeleton formation reaction of benzoylpyridines. The compounds were tested for vasorelaxant activity in tetrathylammonium choloride (TEA) and BaCl
2-induced and high KCl-induced contraction of rat aorta to identify potential K
+ channel openers, and also for oral hypotensive effects in spontaneously htypertensive rats. An electron-withdrawing group with the proper shape at C6 and a methyl or halogeno group at C7 of the 1, 3-benzoxazine nucleus were required for the development of opticmal vasorelaxant and hypotensive activity. In particular, 2-(6-bromo-7-chloro-2, 2-dimethyl-2H-1, 3-benzoxazin-4-yl)pyridine 1-oxide (71) showed more potent vasorelatzant activity (EC
50=0.14 μM) against TEA and BaCl
2-induced contraction and longer-lasting hypotensive effects than cromakalim (1).
View full abstract
-
Shigehiro TAKEGAWA, Naoyuki KOIZUMI, Mamoru MIEDA, Kenyu SHIBATA
1996 Volume 44 Issue 4 Pages
746-748
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
11-Oxachlormadinone acetate (17-acetoxy-6-chloro-11-oxapregna-4, 6-diene-3, 20-dione) and 2, 11-dioxachlor-madinone acetate (17-acetoxy-6-chloro-2, 11-dioxapregna-4, 6-diene3, 20-dione) were prepared as potential antiandrogenic agnets. The effect of the latter compound on antiandrogenic activity when tested in the castrated rat was shown to be more potent than that of the parent compound, chlormadinone acetate.
View full abstract
-
Shoji FUKUMOTO, Zen-ichi TERASHITA, Yasuko ASHIDA, Shinji TERAO, Mitsu ...
1996 Volume 44 Issue 4 Pages
749-755
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Enantiomers of four potent nonprostanoid thromboxane A
2 (TXA
2) receptor antagonists, (±)-7-(4-fluoro-phenyl)-7-(2-hydroxyphenyl)heptanoic acids (1-4), were synthesized stereoselectively by direct ortho-alkylation of phenols under modified Mitsunobu conditions. The reaction of 5 eq of phenols (6a-c) with 1 eq of (S)- or (R)-methyl 7-(4-fluorophenyl)-7-hydroxyheptanoate ((S)-or (R)-y) afforded ortho-alkylated phenol derivatives (6a-c) enantioselectively in 33 to 42% chemical yield and 90 to 93% ee. In these compounds, the (R)-enantiiomers (1-4) exhibited potent TXA
2 receptor antagonistic activity and the (S)-isomer (3) was much less active. In particular, compound (R)-3 strongly inhibited U-46619-induced human platelet aggregation (IC
50=48 nM), and also showed a very potent inhibitory effect with a minimum effective dose (MED) of 0.3 mg/kg (p.o.) on U-46619-induced bronchoconstriction in guinea pigs.
View full abstract
-
Takanobu KUROITA, Masamitsu SAKAMORI, Takeshi KAWAKITA
1996 Volume 44 Issue 4 Pages
756-764
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Several 3-substituted 5-chloro-2-methoxybenzamides were synthesized and evaluated for serotonin-3 (5-HT-3) receptor binding affinity. The 5-HT
3 receptor antagonistic activity of zacopride, a representative 5-HT
3 receptor antagonist, was unchanged by the replacement of the 4-amino substituent on the aromaitc moiety by a 3-dimethyl-amino substituent. This finding prompted a structural modification of azasetron, another 5-HT
3 receptor antagonist. Consequently, a new series of 3, 4-dihydro-2H-1, 4-benzoxazine-8-carboxamides was obtaiend and these compounds were found to be more potent than 3, 4-dihydro-3-oxo-2H-1, 4-bvenzoxazine-8-carboxamids. In particular, (S)-N-(1-azabicyclo[2.2.2]oct-3-yl)-6-chloro-3, 4-dihydro-4-methyl-2H-1, 4-benzoxazine-8-carboxaminde showed a high affinity for 5-HT
3 receptors (K
i=0.051 nM) and especially potent antagonistic activity against the von Bezold-Jarisch reflex (ED
50=0.089 μg/kg i.v.) in rats.
View full abstract
-
Shuniciro SAKURAI, Nobuo OGAWA, Tomio SUZUKI, Ken-ichi KATO, Tetsuo OH ...
1996 Volume 44 Issue 4 Pages
765-777
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
In order to find new antiasthematic and antithrombotic agents, various [[1-aryl(or benzyl)-1-(benzenesulfonamido)methyl]phenyl]alkanoic acids derivatives were synthesized. Evaluation of these compounds for thromboxane A
2 (TXA
2) antagonistic activities indicated that 4-[4-[(4-chlorobenzenesulfonamido)phenylmethyl]phenyl]butyric acid (6h), 4-[4-[1-(4-chlorobenzenesulfonamido)-2-phenylethyl]butyric acid (6y) and many other compounds have potent inhibitory effects on U-46619-induced guinea-pig platelet aggregation. No significant difference in the inhibitory effect between (+)-6h and its antipode could be detected, although (+)-6y was about 10 times more potent than (-)-6y. The pK
b values of 6h and 6y were estimated to be 8.9 and 10, respectively on U-46619-induced contraction of guinea-pig trachea as a pharmacological measure of TXA
2 antagonistic activity. These compounds also showed potent inhibitory effects on U-46619-induced bronchoconstriction in guinea-pig after oral administration in vivo. They were also evaluated for other related pharmacological effects involving the arachidonic acid cascade. It ws found that these compounds possess TXA
2 synthase inhibitory activity together with TXA
2 antagonistic activity, and 6h also possesses weak leukotriene D
4 (LTD
4) antagonistic acitivity. Structure-activity relationships for TXA
2 antagonistic activity of these derivatives are discussed.
View full abstract
-
Mitsuru OHKUBO, Atsuchi KUNO, Kiyotaka KATSUYA, Yoshiko UEDA, Kiyoharu ...
1996 Volume 44 Issue 4 Pages
778-784
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Novel 4, 5, 6, 7-tetrahydrothieno[3, 2-c]pyridines, 1-thienyl-1, 2, 3, 4-tetrahydroisoquinolines and related compounds, in which the benzene rings of (+)-1 (FR115427) were replaced with heteroaromatic rings such as thiophene, furan, benzothiophene and indole, were synthesized and evaluated for anticonvulsant activity against i.c.v. N-methyl-D-Aspartate (NMDA)-induced seizures in mice, Among these compounds, (+)-4-methyl-4-phenyl-4, 5, 6, 7-tetrahydrothieno[3, 2-c]pyridine hydrochloride ((+)-2a), (+)-4-methyl-4-(2-thienyl)-4, 5, 6, 7-tetrahydrothieno[3, 2-c]pyridine hydrochloride ((+)-2g), and (-)-1-methyl-1-(2-thienyl)-1, 2, 3, 4-tetrahydroisoquinoline hydrochloride ((-)-3a) showed significant anticonvulsant activity. The structure-activity relationships with regard to the anticonvulsant activity of this series of compounds are discussed.
View full abstract
-
Hiroshi MIYAUCHI, Koichi KOZUKI, Tomoharu TANIO, Naohito OHASHI
1996 Volume 44 Issue 4 Pages
785-792
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
3-Methyl and 3, 3-dimethyl analogs of 2-(2, 4-difluorophenyl)-3-(ω-substituted alkyl)sulfonyl-1-(1H-1, 2, 4-triazol-1-yl)-2-propanols were synthesized and evaluated for their antifungal activites against Candida aldicans and Aspergillus fummigatus. The 3, 3-dimethyl analogs were found to have more potent activity both in vitro and in vivo than the corresponding 3-mono-methyl analogs. The prophylactic efficacy of the lead compounds against murine systemic candidiasis and aspergillosis was improved signifcantly by dimethylation of the 3-position.
View full abstract
-
Haruko TAKECHI, Seiji KAMADA, Minoru MACHIDA
1996 Volume 44 Issue 4 Pages
793-799
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
7-Dimethylaminocoumarin derivatives were synthesized and the characteristics of their absorption and emission spectra were investigated. Among them, 3-aryl-7-dimethylaminocoumarins were shown to be promising candidates as the fluorogenic groups for highly sensitive derivatization reagents. Based on the spectroscopic studies, 3-[4-(bromomethyl)phenyl]-7-(diethylamino)-2H-1-benzopyran-2-one (MPAC-Br) was designed and synthesized as a fluorescent derivatization reagent for carboxylic acids in HPLC. Saturated carboxylic acids (C
4-C
18) were derivatized almost quantitatively into the corresponding fluorescent MPAC-esters by treatment with MPTAC-Br. The MPAC-esters of these acids were clearly separated on a reversed-phase HPLC column (Intertsil ODS-2, mobile phase : methanol-water, excitation wavelength 403 nm; emission wavelength 474 nm). The detection limit (S/N=17) of lauric acid, as a test compound, was 15 fmol/10 μl.
View full abstract
-
Bei GUO, Jun-ichi ANZAI, Tetsuo OSA
1996 Volume 44 Issue 4 Pages
800-803
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
The adsorption behavior of serum albumin onto the surface of platinum, gold, and glassy carbon electrodes was studied in relation to the electrode potential, by using cyclic volutammetry and a quartz-crystal microbalance. The kinetics of adsorption was significantly dependent on the electrode potential. The adsorption was highly accelerated by the application of positive potential to the electrode, suggesting an electrostatic interaction between the negatively charged alumin molecules and the positively polarized electrode as the origin of the accelerated adsorption. The adsorption of albumin on the electrodes was irreversible with respect to dilution of the albumin solution, while the albumin molecules were desorbed in part upon shifting the electrode potential in the negative direction. The quartz-crystal microbalance data showed that alumin forms a monomolecular layer on the electrode surface. Protein adsorption on electrode surface in serum was also examined.
View full abstract
-
Yuko TAKEMURA, Hisayo KAWAGUCHI, Satomi MAKI, Motoharu JU-ICHI, Mitsuo ...
1996 Volume 44 Issue 4 Pages
804-809
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
A new acridone alkaloid, 1, 3, 5-trihydroxy-10-methylacridone (8), and two new coumarins, trans-clausarinol (9) and khelmarin-D (11), were isolated from the root of Yalaha [several hybrid seedlings resulting from a cross of Duncan grapefruit (Citrus paradisi MACF.)×Dancy tangerine (C. tangerina HORT. ex TANAKA)], and structures were determined on the basis of spectroscopic evidence. Seventy known coumarins, acridone alkaloids and miscellaneous compounds were also characterized.
View full abstract
-
Dongming ZHANG, Toshio MIYASE, Masanori KUROYANAGI, Kaoru UMEHARA, Aki ...
1996 Volume 44 Issue 4 Pages
810-815
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Five new oleanane-type saponins, polygalasaponins XXVIII-XXXII, along with one known saponin, polygalasaponin XXIV, and one known acylated sucrose, tenuifoliside C, were isolated from the root of Polygala japonica. The structuers of these new compounds were elucidated as 3-O-β-D-glucopyranosyl presenegenin 28-O-β-D-xylopyranosyl (1→4)-α-L-rhamnopyranosyl (1→2)-β-D-fucopyranoxyl ester, 3-O-β-D-glucopyranosyl presenegenin 28-O-β-D-galactopyranosyl (1→5)-β-D-apiofuranosyl (1→4)-β-D-xylopyranosyl (1→4)-α-L-rhamno-pyranosyl (1→2)-β-D-fucopyranosyl ester, 3-O-β-D-glucopyranosyl presenegenin 28-O-β-D-galactopyranosyl (1→4)-β-D-xzylopyranosyl (1→4)-α-L-rhamnopyranosyl (1→2)-[4-O-p-methoxycinnamoyl]-[β-D-glucopyranosyl (1→3)]-β-D-fucopyranosyl ester, 3-O-β-D-glucopyranosyl presenegenin 28-O-α-L-arabinopyranosyl (1→3)-β-D-xylopyranosyl (1→4)-[β-D-apiofuranosyl (1→3)]-α-L-rhamnopyranosyl (1→2)-[4-O-3, 4, 5-trimethoxycinnamoyl]-β-D-fucopyranosyl ester, 3-O-β-D-glucopyranosyl presenegenin 28-O-α-L-arabinopyranosyl (1→3)-β-D-xylopyranosyl (1→4)-[β-D-apiofuranosyl (1→3)]-α-L-rhamnopyranosyl (1→2)-[4-O-p-methoxycinnamoyl]-[α-L-rhamnopyranosyl (1→3)]-β-D-fucopyranosyl ester, erspectively, on the basis of spectroscopic and chemical evidence.
View full abstract
-
Chieko TANI, Yukio OGIHARA, Motoo MUTUGA, Takatoshi NAKAMURA, Tadahiro ...
1996 Volume 44 Issue 4 Pages
816-822
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Six new triterpenoidal saponins, called calliandra saponins G(1), H(2), I(3), J(4), K(5) and L(6), were isolated from the branches of Calliandra anomala (KUNTH) MACBR. THe structuers of these compounds were established on the basis of NMR spectra, FAB-MS, and chemical evidence. These saponins, interestingly, have an N-Acetyl glucosamine at the 3 position of the genin, and one or two monoterpene glycosides at the position of the sugar chain.
View full abstract
-
Osami TAKEDA, Eiji MIKI, Susumu TERABAYASHI, Minoru OKADA, Shan-an HE, ...
1996 Volume 44 Issue 4 Pages
823-828
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
To elucidate the variation of essential oli components in the rhizomes of Atractylodes lancea growing in China we used nine clones of the species, which were propagated by division of the rhizomes, and characterized them by means of GC analyses of the six essential oil components. The seasonal changes in the components were also investigated for 3 years using one of the clones. These clones contained β-eudesmol (4) and hinesol (3) as the main components and the values of the correlation coefficients between 4 and 3 were more than 0.9 in every clone. Although the amount of each component varied in a clone, the value of the content ratio between the components was constant during growth of the plants for 3 years and each clone had a different ratio value. These results indicated that the biosynthetic ratio could be genetically determined. Implications of the variation in the components of this species in its native habitat were also discussed.
View full abstract
-
Hiroshi KURAHASHI, Hiroshi KAMI, Hisakazu SUNADA
1996 Volume 44 Issue 4 Pages
829-832
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
An examination was made of the release of isoniazid, anhyrous caffeine, theophylline, salicylic acid and indomethacin from hydroxypropylmethylcellulose (HPMC) matrices, and the results were usually found to follow first order kinetics. the release rate of the drug was influenced by the solubility of the drug, and by the viscosity and the content of HPMC. As the drug solubility increased, the drug release rate also increased, and conversely, as the viscosity and/or the content of HPMC increased, the drug release rate decreased. A multiple regression analysis was used to determine the relationship between response (release rate) and factors (drug solubility, HPMC viscosity and HPMC content), and a statistically significant model was obtained. This model allows not only predictions of the drug release rate from HPMC matrices, but also establishment of the formulation of the target drug without experimental determination.
View full abstract
-
Daiichi WATANABE, Masato OHTA, Zhi Jun YANG, Etsuo YONEMOCHI, Toshio O ...
1996 Volume 44 Issue 4 Pages
833-836
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
The complexes of heptakis-(2, 6-di-O-methyl)-β-cyclodextrin (DMβCD) and p-nitrophenol (p-NP), which were prepared by sealed-heating and a slow evaporation method, were comparatively evaluated. From the results of differential scaning calorimetry, powder X-ray diffraction, and infrared spectroscopy, the sealed-heated sample was considered as a new complex which was different from the slow evaporation complex. Also, the data from a sublimation experiment indicated that the inhibition of sublimation of p-NP was observed only in the sealed-heated sample. These results suggested that p-NP molecules were included within the cavity of DMβCD molecules, whereas in case of the slow evaporation complex, p-NP molecules were located in the intermolecular space among the DMβCD molecules.
View full abstract
-
Fude CUI, Yoshiaki KAWASHIMA, Hirofumi TAKEUCHI, Toshiyuki NIWA, Tomoa ...
1996 Volume 44 Issue 4 Pages
837-842
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Acrylic polymer (Eudragit-RS 100 or -RS PM) microspheres of acebutolol hydrochloride, a highly water soluble model drug, were prepared by the polymeric shpherical crystallization technique with a good slvent (acetone + ethanol), a bridging liquid (water) and a poor slvent (cyclohexane) system. The microspheres were produced through coacervation of the drug and polymer in quasi-emulsion droplets of the good solvent and the birdging liquid mixture, but were dissolved when dispersed in the poor solvent. The preparation mechanism and the ratios of solvents employed for inducing the coacervation were determined by constructing a solubility phase diagarm of the polymer in the good and poor solvent systems. To improve the sustained releasing properties of the microspheres, they were coated directly with sodium alginate powder in the same preparation batch of microspheres. The treatments of the microspheres and coated microspheres with triethyl citrate significantly retarded the drug release rates from each due to the improved embedding of the drug in the polymer. Whewn they were formulated into capsules or tablets, the drug release rates were prolonged much further because of their gelled matrix structures formed during dissolution. The drug release mechanism was described by the square root time model by the diffusion of drug through the gelled layer of polymer.
View full abstract
-
Nobutoshi TANAKA, Ken-ichi HOSOI, Daizo TANAKA, Mimei TAKAHASHI
1996 Volume 44 Issue 4 Pages
843-846
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Chemical properties of ergosta-4, 6, 8(14), 22-tetraen-3-one (1) were investigated. Though 1 is rather stable to acids or bases, it reacts easily with two moleculres of oxygen on irradiation with UV light to give 6α, 9α-epidioxy-14α-hydroperoxyergosta-4, 7, 22-trien-3-one (2), which is transformed successively to 6α, 7α;8α, 9α-diepoxy-14α-hydroperoxyergosta-4, 22-dien-3-one (3) and 14α-hydroperoxy-9α-hydroxyergosta-4, 7, 22-triene-3, 6-dione (4) under these reaction conditions.
View full abstract
-
Haruo NUKAYA, Hirokazu YAMASHIRO, Hirotatsu FUKAZAWA, Hitoshi ISHIDA, ...
1996 Volume 44 Issue 4 Pages
847-849
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Triterpene carboxylic acids were isolated from the methanol extract of Hoelen, Poria cocos, and found to inhibit 12-O-tetradecanoylphorbol 13-acetate (TPA)-induced mouse ear edema. Their chemical structures were identified as 3β, 16α-dihydroxylanosta-7, 9(11), 24-trien-21-oic acid, 16α-hydroxydehydropachymic acid, 16α-hydroxytrametenolic acid and dehydrotumulosic acid.
View full abstract
-
Nobuya KATAGIRI, Masashi MAKINO, Takahiro TAMURA, Chikara KANEKO
1996 Volume 44 Issue 4 Pages
850-852
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Asymmetric induction was observed in the hetero Diels-Alder reaction of benzenesulfonly cyanide with cyclopentadiene using chiral Lewis acids. This is the first instance of asymmetric Diels-Alder reaction involving a sulfonyl group in the presence of a chiral Lewis acid.
View full abstract
-
Masumi TAKEMOTO, Yuichi YAMAMOTO, Kazuo ACHIWA
1996 Volume 44 Issue 4 Pages
853-855
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
The stereochemical course of the reduction of benzoylpyridine derivatives (1a-e) by baker's yeast can be modified by immobilization or by treating the reduction system with allyl alcohol or ethyl chloroacetate.
View full abstract
-
Tetsushi YAMASHITA, Eiji HATAMOTO, Hiroshi TAKENAKA, Yoshitane KOJIMA, ...
1996 Volume 44 Issue 4 Pages
856-859
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
The amide and ester carbonyl groups of four pipierazin-2-one derivatives (N, N'-ethylene-bridged dipeptide ethyl esters) constructed from (R)- or (S)-phenylalanine and glycine were reduced with borane-tetrahydrofuran complex to produce the corresponding piperazine derivatives in 70-80% yields. These piperazin-2-one or piperazine derivatives were used as the carboxyl-terminal residues of eight dermorphin analogues (H-tyrosyl-D-alanyl-piperazin-2-one or piperazine derivatives) whose opiate activities were examined in vitro by use of the guinea pig ileum and the mouse vas deferens assays. It was found in the guinea pig ileum assay that the configuration of phenylalanine and the replacement of the piperazin-2-one ring with a piperazine ring are important for enhancing or reducing the opiate activities of these analogues.
View full abstract
-
Bei GUO, Jun-ichi ANZAI, Tetsuo OSA
1996 Volume 44 Issue 4 Pages
860-862
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
The surface of a glassy carbon (GC) electrode was modified covalently with ethyleneglycol, diethyleneglycol, 1, 2-propanediol, and 1, 3-propanediol by electrochemical oxidation in order to suppress the electrode fouling originating from non-speific adsorption of serum proteins. Human serum albumin (HSA) was adsorbed significantly on the surface of a bare GC electrode, which was monitored by cyclic voltammetry in the presence of Fe(CN)
4-6/Fe(CN)
3-6 ions. In contrast, the diol-modified GC electrodes were sccarcely fouled in HSA solution and even in human serum.The results were explained reasonably based on teh hydrophilic nature of the diol-modified GC surface.
View full abstract
-
Tenji KONISHI, Teppei OTANI, Shiu KIYOSAWA, Yasuhiro FUJIWARA
1996 Volume 44 Issue 4 Pages
863-864
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Two compounds related to amino acid amides, named euscamines A and B, have been isolated from the capsule of Euscaphis japonica (THUNB.) KANTIZ together with three known triterpenoic acids. Euscamines A and B were established as N-(3'-hydroxymethyl-2', 5'-dihydro-2'-furyl)-succinamic acid and N
5(3'-hydroxymethyl-2', 5'-dihydro-2'-furyl)-N
5-methyl-glutamine methyl ester, respectively.
View full abstract
-
Masayuki ENDO, Takeshi YAMAMOTO, Tomoko IJUIN
1996 Volume 44 Issue 4 Pages
865-867
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
The effect of 14 types of nonionic surfactants on the permeation of Tenoxicam (TEN) through guinea pigs from propylene glycol solution was investigated in vitro. The flux of TEN was significantly enhanced by polyoxyethylene alkyl ether and polyoxyethylene monoalkyl carboxylate as hydrophilic surfactants, and by polyglyceryl trialkylate, glyceryl monoalkylate, sorbitan monoalkyl carboxylate and sorbitan trialkyl carboxylate as hydrophobic surfactants. In the presence of these surfactants, the flux was increased about 2 to 4 times, as compared to the flux without them. The mechanism of nonionic surfactant action was analyzed and classified by recent methods, the including HLB of surfactants, the solubility of the durgs in vehicle and the hemolysis of erythrocytes. The rersults suggested that vital factors in the enhancement of skin permeation by nonionic surafctants include the affinity of the surfactants to the stratum corneum, the solubility of the drugs in vehicle and the penetration of surfactants to the stratum corneum.
View full abstract
-
Kiyoshi TAKAMI, Hitoshi MACHMURA, Kenemasa TAKADO, Michiji INAGAKI, Yo ...
1996 Volume 44 Issue 4 Pages
868-870
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Free flowing spherically granulated (average diameter, 70 or 115 μm) dibasic calcium phosphate anhydrous (DCPA) for direct tabletting was prepared by a restricted crystal growing synthesis of DCPA, followed by spray drying of its aqueous dispersions. The spherically granulated DCPA had larger specific suraface area (32 to 34 m
2/g), because they had porous structures compoesd of very fine primary crystals (Heywood diameter, 0.1-1.0 μm) compared to conventionally prepared DCPA (Heywood diameter, 2.0-5.0 μm). The crystallinity of granulated DCPA was lower than that of conventional DCPA. Those micromeritic characteristics of granulated DCPA might correlated closely with their dramatically improved tablettability.
View full abstract
-
Yoshio OKADA, Jidong WANG, Takeshi YAMAMOTO, Yu MU
1996 Volume 44 Issue 4 Pages
871-873
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
N
π-1-Adamantyloxymethylhistidine, His(N
π-1-Adom) was prepared, and the properties of the 1-Adom group were examined. 1-Adom group can be easily removed by TFA ; it is stable to 20% piperidine/DMF and 1N NaOH. His(N
π-1-Adom) derivatives can suppress racemization during coupling reaction. TRH was synthesized using His(N
π-1-Adom), successfully.
View full abstract
-
Hui Li ZHANG, Akito NAGATSU, Jinsaku SAKAKIBARA
1996 Volume 44 Issue 4 Pages
874-876
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Three novel antioxidative serotonin derivatives were isolated from safflower oil cake (Carthamus tinctorius L.). Their structures were established as 4, 4"-bis(N-p-coumaroyl)serotonin (1), 4-[N-(p-coumaroyl)serotonin-4"-yl]-N-feruloyserotonin (2), and 4, 4"-bis(N-feruloyl)serotonin (3). Antioxidative activities of the compounds were measured by ferric thiocyanate method and DPPH method, and the compounds showed strong antioxidative activity.
View full abstract
-
Tadashi HASHIMOTO, Susumu SAITO, Kazuhiro OHKI, Naoki SAKURA
1996 Volume 44 Issue 4 Pages
877-879
Published: April 15, 1996
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Highly selective cleavage reaction of pGlu-peptide bond is described. Two model peptides, pGlu-X-Ala-Phe-OH (X=Ile and Ser), and dog neuromedin U-8 (d-NMU-8) (1-7)-OH (pGlu-Phe-Leu-Phe-Arg-Pro-Arg-OH) were hydrolyzed in concentrated HCl at 0°C for from 6 days to 6 weeks to give the predominant cleavage products of pGlu-X linkage of pGlu-X-Ala-Phe-OH and the pGlu-Phe linkage of d-NMU-8 (1-7)-OH, respectively. The ring-opening reaction of the pyrrolidone moiety of the pGlu residue occurred to a considerably lesser extent.
View full abstract