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Goro Kobayashi, Sunao Furukawa
1964 Volume 12 Issue 10 Pages
1129-1135
Published: October 25, 1964
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Several 3-phenyl-9H-pyridazino[3, 4-b]indoles were prepared by heating 3-phenacyl-oxindoles and hydrazine hydrate in acetic acid solution.
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Kunio Nakagawa, Hiroshi Onoue, Jitsuo Sugita
1964 Volume 12 Issue 10 Pages
1135-1138
Published: October 25, 1964
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Nickel peroxide, readily obtainable by the treatment of an aqueous solution of nickel sulfate with sodium hypochlorite in an alkaline solution, was shown to be a useful oxidizing agent for a preparation of substituted 2-phenylbenzoxazoles from the corresponding Schiff's bases in benzene or ether.
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Masahiro Nakadate, Chikako Matsuyama, Michiya Kimura
1964 Volume 12 Issue 10 Pages
1138-1143
Published: October 25, 1964
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This work was undertaken to obtain a more satisfactory reagent for the assay of active methylene compounds than has been used. Biphenyl, diphenylmethane, diphenyl ether, diphenyl sulfide, diphenylsulfone and stilbene with nitro groups in 4, 4'-, 2, 4-, 2, 2', 4, 4'-positions were prepared and their color reactions with acetone and cyclohexanone in the presence of alkali were examined. 4, 4'-Dinitro compounds gave negative Janovsky reaction. Bis(p-nitrophenyl)-(IV) and bis(2, 4-dinitrophenyl)methane (V) gave blue color in methylcellosolve with addition of alkali without active methylene compound. 2, 4-Dinitro compounds showed bathochromic shift as compared with usual reagents such as m-dinitrobenzene, 1, 3, 5-trinitrobenzene and picric acid. The intensities of colors by these reagents were lower. 2, 2', 4, 4'-Tetranitro compounds showed higher intensities and sufficient stabilities of the color produced, but no bathochromic shifts. These tetranitro compounds also gave the specific color reactions for active methylene compounds such as acetone, cyclohexanone, 17-ketosteroids, creatinine and cardiac glycosides. 2, 2', 4, 4'-Tetranitrobiphenyl (III) could be the reagent that has higher sensitivity, sufficient stability and specificity in color reaction of active methylene compounds with alkali.
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Tamotsu Okumura, Yoshio Nozaki, Daisuke Satoh
1964 Volume 12 Issue 10 Pages
1143-1151
Published: October 25, 1964
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Through the microbiological transformation of 3β, 14, 21-trihydroxy-14β-pregnan-20-one (III) and 4, 5-dehydrodigitoxigenone (IV) by Absidia orchidis, several kinds of products were isolated, and the structure and configuration of three hydroxylated products, one from III and two from IV, were clarified ; 1β, 3β, 14, 21-tetrahydroxy-14β-pregnan-20-one (V), 7β, 12β-dihydroxy-4, 5-dehydrodigitoxigenone (VIII), and 7β-hydroxy-4, 5-dehydrodigitoxigenone (IX). Based on these experimental results, the relationships between the structure of substrate and the positions to be hydroxylated in the microbiological transformation of cardiac aglycone derivatives by A.orchidis were discussed.
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Tadashi Watabe, Hidetoshi Yoshimura, Hisao Tsukamoto
1964 Volume 12 Issue 10 Pages
1151-1158
Published: October 25, 1964
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Interesting selective demethylation of brucine and 4-substituted veratroles, which was found to occur as major metabolism in rabbits, was further investigated by in vitro systems. Using 9000×g. supernatant fraction of rabbit liver homogenate, it was shown that demethylation of brucine and 4-nitroveratrole was catalyzed by so called "liver microsomal drug metabolizing enzyme systems, " and it took place predominantly at the meta-position of the lactam group of brucine and at the para-position of nitro group of 4-nitroveratrole at pH 7.5, coinciding with the in vivo results.
1, 2 On the other hand, 4-acetamidoveratrole underwent mostly deacetylation by the same fraction. In addition, demethylation of 4-nitroveratrole studied further by rabbit liver microsomes, and it was found that NADH was even more effective than NADPH as the cofactor if added sufficiently to the incubation mixture.
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Kakuichi Sakai
1964 Volume 12 Issue 10 Pages
1159-1163
Published: October 25, 1964
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A marked decrease in impulse count which is produced by bitter substances when tongue (frog) was pretreated with AChE. It was assumed that there is a close relationship between AChE and the sensation of bitter taste. Factors affecting the strength and durability of bitter taste were discussed.
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Hiroshi Kugita, Mikio Takeda
1964 Volume 12 Issue 10 Pages
1163-1166
Published: October 25, 1964
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dl-2'-Methoxy-9β-hydroxymethyl-2, 5-dimethyl-6, 7-benzomorphan was synthesized by hydroboration of 2'-methoxy-9-methylene-2, 5-dimethyl-6, 7-benzomorphan. The β-orientation of the hydroxymethyl group was established by converting IV to the known 9β-methyl derivative. Dehydration of 2'-methoxy-9-hydroxy-2, 5, 9-trimetyl-6, 7-benzomorphan (I) to the 9-methylene derivative (II) produced also a rearrangement product isomeric with II.
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Hiroshi Kugita, Mikio Takeda
1964 Volume 12 Issue 10 Pages
1166-1171
Published: October 25, 1964
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The addition of borane to 9-methylenebenzomorphan at high temperature has been examined in the hope of clarifying stereochemical course of the hydroboration which gave selectively the 9β-hydroxymethyl derivative in the previous study. Reaction of pyridine-borane with I in benzene at 70° gave the benzomorphan-borane (II) in high yield. Heating II in anisole followed by the oxidation gave the 9α-hydroxymethyl derivative (IV) along with the 9βisomer and a neutral product (V). The formation of 9α isomer was rationalized in terms of the dissociation of the amine-borane prior to the addition of borane to the double bond. α-Orientation of the 9-hydroxymethyl group of IV was established by converting IV to the known dl-2, 5, 9α-trimethylbenzomorphan (VIII) via the toluene-p-sulfonate (VII).
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Hiroshi Kugita, Mikio Takeda
1964 Volume 12 Issue 10 Pages
1172-1175
Published: October 25, 1964
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The stereochemical course of the borane addition to 9-methylenebenzomorphan leading to the 9β-hydroxymethyl derivative was further examined. Formation of the intramolecular coordinated amineborane (A) was observed by the reaction of diborane with both the free amine (I) and the benzomorphan-borane (II). That the first one mole of boron hydrides adds to I at the nitrogen to give the amineborane (II) without addition to the double bond was also established. Isolation of intermediates in alkylborane stage was attempted.
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Yasuo Inubushi, Hisashi Ishii, Bompei Yasui, Takeshi Konita, Takashi H ...
1964 Volume 12 Issue 10 Pages
1175-1180
Published: October 25, 1964
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From the Chinese drug "Chin-Shin-Hu" imported from Hong Kong, two tertiary bases were isolated. One is dendrobine, first isolated by H. Suzuki, et al.
2) and the second is a new base which has not previously been reported in the literature, for which the name dendramine is proposed. The water soluble alkaloid was also examined and it was concluded that the quaternary alkaloid found in this drug is the N-methyl dendrobium salt.
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Shunsaku Noguchi, Fujiko Nakayama, Katsura Morita
1964 Volume 12 Issue 10 Pages
1180-1183
Published: October 25, 1964
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21-Hydroxymethyl-Reichstein's substance S (III), 21-hydroxymethyldexamethasone (IV ), 21-hydroxymethyldeoxycorticosterone (VI) and 21, 21-bis(hydroxymethyl)deoxycorticosterone (VII) were synthesized by the aldol condensation of the parent steroids with formaldehyde in the presence of sodium acetate. When 21-hydroxymethyl-Reichstein's substance S diacetate (VIII) and 21-hydroxymethyldeoxycorticosterone diacetate (X) were passed through a column of alumina, 21-methyl-17α-hydroxypregn-4-ene-3, 20, 21-trione acetate(IX) and 21-methylpregn-4-ene-3, 20, 21-trione (XI) were obtained. The diketone (XI) underwent further decomposition in the air to give androst-4-ene-3, 17-dione.
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Shunsaku Noguchi, Masayuki Imanishi, Katsura Morita
1964 Volume 12 Issue 10 Pages
1184-1188
Published: October 25, 1964
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Treatment of 16β, 20α-dihydroxysteroids, Ia, Ib, and Ic, with Na
2Cr
2O
7-H
2SO
4 reagent in ether-benzene-tetrahydrofuran resulted in a selective oxidation of the 16-hydroxyl group to afford 20α-hydroxy-16-oxosteroids, IIIa, IIIb, and IIIc. IIIa, IIIb, and the 20-acetates, IVa and IVb, were treated with TsCl, KHCO
3, K
2CO
3 or alumina to afford a mixture of cis and trans 17(20)-16-oxosteroids (V and VI). The C-20 configuration of the isomers, V and VI, was established on the basis of the nuclear magnetic resonance spectra.
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Shunsaku Noguchi, Masayuki Imanishi, Katsura Morita
1964 Volume 12 Issue 10 Pages
1189-1192
Published: October 25, 1964
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5'-Methyl-5α-androstano[16, 17-c]isoxazolin-3β-ol (Va) and 5'-methylandrost-5-eno[16, 17-c]isoxazolin-3β-ol (Vb), were obtained by treatment of 3β, 20α-dihydroxy-5α-pregnan-16-one 3-acetate 16-oxime (IIIa) or 3β, 20α-dihydroxypregn-5-en-16-one 3-acetate 16-oxime (IIIb) with tosyl chloride in pyridine followed by alkaline hydrolysis. Oxidation of Va and Vb gave the corresponding 3-oxo-compounds, VIa and VIb. VIb was further isomerized to 5'-methylandrost-4-eno[16, 17-c]isoxazolin-3-one (VIIb).
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Keiji Sekiguchi, Keiji Ito, Eiji Owada, Keihei Ueno
1964 Volume 12 Issue 10 Pages
1192-1197
Published: October 25, 1964
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The mechanism of the size reduction of griseofulvin to micron grade caused by exposing to liquid or vaporous chloroform and then removing it in a vacuum at higher temperatures was investigated by the differential thermal and thermo-gravimetric analysis. The results indicate that a solvated compound having a molar composition of 1 : 1 is formed between the antibiotics and chloroform. It becomes clear that the formation and decomposition of the solvate play an important role in reducing particle size, since lattice rearrangement to the solvate and back to the original compound is occurred during these processes, and the growth of larger crystals is prevented by the difficulty of migration of the newly formed molecules to the nuclei in the solid state. The "solvation and desolvation" method of size reduction first acquired practical success in the production of finely powdered griseofulvin is thought to find application to other materials, since the processes involved are simple, effective and economical.
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Kozo Nagano, Hisashi Kinoshita, Akiko Hirakawa
1964 Volume 12 Issue 10 Pages
1198-1206
Published: October 25, 1964
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The following complexes were isolated by mixing metal chloride and ligand in water or ethanol. Their composition formulae were determined from the data of elemental analyses and their complex types are shown in parentheses. INH-Cu(MZ) ; INH-Cd(M(HZ)
2) ; NH-Cu(MZ) ; PH-Cu(MHZ and MZ) ; BH-Cu(MHZ) ; BH-Cd(MHZ); PNBH-Cu(MZ) ; INA-Cu(M(HZ)
2) ; N-Me-INH-Cu(MHZ) ; NA-Cu(M(HZ)
2) ; PA-Cu(MHZ). The infrared spectra of these complexes were investigated by comparing with those of ligands themselves and those of N-deuterated metal complexes. The behavior of the main hands (the bands of amide I, II, and III, NH
2 deformation and pyridine ring vibrations) were discussed in relation to the structure of the complexes and their constitutional formulae were postulated.
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Kozo Nagano, Hisashi Kinoshita, Akiko Hirakawa
1964 Volume 12 Issue 10 Pages
1207-1217
Published: October 25, 1964
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To give reliable assignments for infrared spectra of metal complexes of isonicotinoylhydrazine and related compounds, the spectra of ligands themselves, their N-deuterated derivatives, their hydrochlorides and their N-deuterated hydrochlorides were investigated. The bands of amide, NH
2 deformation and pyridine ring vibrations were determined carefully, and some effective supports could be given to the assignments described in Part IV.
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Kikuo Yasuda
1964 Volume 12 Issue 10 Pages
1217-1224
Published: October 25, 1964
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Some 2-ethoxalyl-4-en-3-one was treated with N-halo-succinimide in pyridine to give the corresponding 2α-halo-4-en-3-one in a good yield. Direct chlorination of testosterone acetate with sulfuryl chloride (1 mole) gave a small amount of 2α-chlorotestosterone acetate in dry beozene or dry ether, and with sulfuryl chloride (excess) gave mainly 2α, 4-dichlorotestosterone acetate in dry benzene and mainly 2α, 6β-dichlorotestosterone acetate in dry ether. These observations were confirmed by the syntheses of their related compounds through the unequivocal routes.
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Hiromu Mori
1964 Volume 12 Issue 10 Pages
1224-1231
Published: October 25, 1964
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The Grignard reaction of 3β-hydroxycholest-4-en-6-one (V) was undertaken in the presence of cuprous chloride or cupric acetate. 1, 4-Addition product was isolated, and its structure was proved to be 3β-hydroxy-4β-methyl-5α-cholestan-6-one (VI). Some transformations related to this compound were made. From observations of the Grignard reaction and other reactions of α, β-unsaturated steroidal ketones reported in literature, it may be concluded that the configuration of alkyl group newly introduced by 1, 4-addition should be axially oriented.
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Toshio Miyazaki, Susumu Mihashi
1964 Volume 12 Issue 10 Pages
1232-1235
Published: October 25, 1964
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From the methanolic extract of the leaves of Boenninghausenia albiflora MEISSNER var. japonica S. SUZUKI, a new coumarin, named matsukaze-lactone (I), C
20H
14O
6, m.p. 267∼268°, was isolated. Methylation of I with dimethyl sulfate and methanolic alkali gave an acid (IIa), C
22H
22O
8, which was oxidized to an acid (IIIa), C
18H
18O
8. By decarboxylation of IIIa with copper powder, 2, 2', 4, 6'-tetramethoxybiphenyl (V) was obtained. From these results, the structural formula (Ia), (Ib) and (Ic) were proposed for matsukaze-Iactone.
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Toshio Miyazaki, Susumu Mihashi, Kinji Okabayashi
1964 Volume 12 Issue 10 Pages
1236-1239
Published: October 25, 1964
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A mixed Ullmann reaction of methyl 3-iodo-(Xb) and 5-iodo-2, 4-dimethoxybenzoate (XIb) gave dimethyl 2, 4', 6, 6'-tetramethoxy-3, 3'-biphenyldicarboxylate (VI), m.p. 164∼166°. It was proved to be identical with an ester (IIIb) which was derived from matsukazelactone (I). Consequently, matsukaze-lactone was represented by formula (Ic), 7, 7'-dimethoxy-6, 8'-bicoumarin and its biogenesis undoubtedly involves oxidative coupling.
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Hatsuhiko Mizuno, Harumi Okuyama, Hikoya Hayatsu, Tyunosin Ukita
1964 Volume 12 Issue 10 Pages
1240-1246
Published: October 25, 1964
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The reaction of aqueous ethylene oxide, a biologically important alkylating agent, with 1-methylcytosine (I) was investigated. At pH above 5, a hydroxyethylation was found to take place at N
3-position of I to yield 1-methyl-3-(2-hydroxyethyl)cytosine (II). When the pH of the reaction mixture was higher than 7, the reaction was followed by a further alkylation at the N
4-position of II to give 1-methyl-N, 3-bis(2-hydroxyethyl)-cytosine (III) and was also followed by hydrolysis of these products, II and III, to 1-methyl-3-(2-hydroxyethyl) uracil (IV). Mechanisms of these reactions are discussed in the light of reaction-rate differences at various pH's. At pH 14, II underwent Dimroth rearrangement to give 1-methyl-N-(2-hydroxyethyl)cytosine (V).
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Itiro Yosioka, Kan Ueda
1964 Volume 12 Issue 10 Pages
1247-1249
Published: October 25, 1964
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Bei der Bromierung mit 1 Mol N. B. S. von 1- und 2-Methyl-phenazin wurde die Methyl-gruppe bromiert und es ergab sich 1-Brommethyl- und 2-Brommethyl-phenazin. Bei der mit 2 Mol N. B. S. von 1-Methylphenazin entstand 1-gem-Dibrommethylphenazin, das sich durch Hydrolyse mit konzentrierter Schwefelsaure 1-Phenazin-aldehyd ergab.
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Toshio Kawasaki, Itsuo Nishioka
1964 Volume 12 Issue 10 Pages
1250-1253
Published: October 25, 1964
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Two saponins (I) and (II) which are detected by conventional paper chromatography of the seed saponins of Digitalis purpurea L. (commercial "digitonin") were isolated by column chromatography on alumina and it was found that I is composed of three tetraglycosides, desglucotigonin, gitonin (m.p. 238∼241°(decomp.), [α]
20
D-60.0°) and desglucodigitonin (m.p. 243∼245°(decomp.), [α]
20
D-71.4°), while II is a mixture of two pentaglycosides, digalonin and digitonin.
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Toshio Nambara
1964 Volume 12 Issue 10 Pages
1253-1258
Published: October 25, 1964
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The chromium trioxide oxidation of 3β, 12α-dihydroxy-5α-androstan-17-one diacetate in glacial acetic acid has been examined and one of the main products isolated has proved to be 3β, 5ξ, 12α-trihydroxyandrostan-17-one 3, 12-diacetate. The preparation of enol acetates derived from epimeric 3β, 12-dihydroxy-5α-androstan-17-ones is also described.
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Zen-ichi Horii, Takefumi Momose, Yasumitsu Tamura
1964 Volume 12 Issue 10 Pages
1262-1264
Published: October 25, 1964
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Fumio Yoneda, Yoshihira Nitta
1964 Volume 12 Issue 10 Pages
1264-1268
Published: October 25, 1964
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Hisashi Tanaka, Osamu Yamauchi
1964 Volume 12 Issue 10 Pages
1268-1269
Published: October 25, 1964
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