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TETSUJI KAMETANI, HARUHIKO YAGI, KIYOSHI KAWAMURA, TETSUYA KOHNO
1970 Volume 18 Issue 4 Pages
645-650
Published: April 25, 1970
Released on J-STAGE: March 31, 2008
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At first the synthetic method of 6-hydroxy-1-(3-hydroxy-2-methoxybenzyl)-5-methoxy-2-oxindole (IIIa) was investigated as a precursor for Amaryllidaceae alkaloids. Secondly phenolic oxidative coupling of IIIa with ferric chloride or potassium ferricyanide under a variety of conditions, but failed.
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SHUNICHI NAITO, SACHIKO BESSHO
1970 Volume 18 Issue 4 Pages
651-655
Published: April 25, 1970
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Stability tests of 4-(aminoethanesulfonylamino) antipyrine in solution were made at different pH's, and it was observed that the chemical in aqueous solution was practically stable at room temperature through kinetical studies.
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THEODORE R. BATES, JOSEPH GALOWNIA, WILLIAM H. JOHNS
1970 Volume 18 Issue 4 Pages
656-662
Published: April 25, 1970
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A three-compartment in vitro transport model, consisting of two aqueous compartments (buffered at pH 1.2 and 7.4) separated by a thin, olive oil-impregnated Millipore membrane, was employed to study the transport kinetics of four drugs in the absence and presence of the complexing agent, caffeine. The test drugs under investigation were salicylic acid, acetylsalicylic acid, dehydroacetic acid, and ethyl p-hydroxybenzoate. The apparent first-order transfer rate constants obtained for the drugs alone were found to correlate well with reported in vivo apparent first-order absorption rate constants. In the presence of caffeine the rate of transfer of all of the test drugs was significantly reduced. Calculated in vitro transport rate constants were found to correlate well with reported in vivo absorption rate constants for the drug-caffeine complexes.
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MAMORU SUGIURA, TARO OGISO
1970 Volume 18 Issue 4 Pages
663-670
Published: April 25, 1970
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In order to clarify the effect of the products formed during lipolysis by Mucor lipase, some experiments were done. The lipase was inhibited by soaps of long-chain fatty acids above C
12, while the lipase was little affected by soaps of C
4-C
8 fatty acids, glycerin and monoglycerides. Long-chain fatty acids in very low concentration, less than 5 μmoles, acted as a competitive inhibitor. Although diffusion of oleic acid from the interface was arrested by laurate and oleate because of the accumulation of the salts at the interface, by the addition of bile salt to the system diffusion of oleic acid was promoted. Bile salts reduced inhibition by long-chain fatty acids, consequently the initial rate of the reaction did not reduce for some time. Ca
2+ also prevented the inhibition by removing the fatty acids into the oil phase after the formation of Ca-soaps.
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ISAO SEKI
1970 Volume 18 Issue 4 Pages
671-676
Published: April 25, 1970
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One-step preparation of the pyrrolidinyl dienamine and the enol ethers including thebaine, which is only known Δ
6, 8-diene compound in the morphine alkaloids, from O, N-disubstituted-normorphinones including codeinone were described. The Δ
6, 8-diene compounds were oxidized to O, N-disubstituted-14-hydroxy-normorphinones with 30% hydrogen peroxide in formic acid.
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MASAKAZU ARITOMI, TOSHIO KAWASAKI
1970 Volume 18 Issue 4 Pages
677-686
Published: April 25, 1970
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On treatment of some C-and O-D-glucopyranosides with diazomethane in methanol or in methanol-dimethylformamide mixture, a partial methylation of the sugar moiety took place, though to a slight extent, to give a mixture of methyl ethers, in which 3-methyl ether is the major. The reaction is much favored in the presence of a small amount of stannous chloride. A O-α-D-glucopyranoside gave almost exclusively the corresponding 3-methyl ether of the glucose residue, while the β-anomer provided, beside 3-methyl ether, 2, 3-dimethyl ether nearly in equal amount. The benzylidene derivatives of O-α-and β-D-glucosides gave also the corresponding 3-methyl ether but 2, 3-dimethyl ether was formed only in trace and, instead, 2-methyl ether was provided.
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GENICHIRO OSHIMA, KINZO NAGASAWA
1970 Volume 18 Issue 4 Pages
687-692
Published: April 25, 1970
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Mercury (II) is able to quench the fluorescence of Rhodamine B in the presence of potassium iodide. The quenching was affected by pH of the solution and the concentration of potassium iodide, but not markedly by several anions. The degree of quenching was closely correlated with mercury (II) concentrations at the fixed concentrations of the dye and potassium iodide, so that mercury (II) can be fluorometrically determined in this method. Cystline and egg albumin protected the quenching by mercury (II) in the presence of potassium iodide. The fluorescence of Rhodamine B was not quenched by organic mercury (II) compounds in the presence of potassium iodide. Fluorescence of the dye was also quenched by some metal ions, such as bismuth (III), thallium (III), palladium (II) and platinum (IV) in the presence of potassium iodide.
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YUKIO SUGIURA, AKIRA YOKOYAMA, HISASHI TANAKA
1970 Volume 18 Issue 4 Pages
693-701
Published: April 25, 1970
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This study was initiated to study on the relationship between the chelate formation and the detoxication activity of penicillamine against heavy metal poisoning. The equilibrium of acid dissociation and the mode of the coordination of metal chelates were investigated by means of potentiometric titration, ultraviolet-visible spectra and proton magnetic resonance spectra. The equilibrium constants among various chemical species of penicillamine in aqueous solution were determined and the results were comparable with those in cysteine. The mode of coordination between penicillamine and metal ions was deduced through the comparison of the formation constants and the absorption spectra of the metal chelates of penicillamine with those of the related compounds. In the chelates produced from penicillamine with Co
2+, Zn
2+ and Ni
2+, the coordination occurs through sulfur and nitrogen atoms while the carboxyl group remains off in coordination, and in the chelates produced from penicillamine with Hg
2+, Cd
2+ and Pb
2+, sulfur, nitrogen and also oxygen atoms contribute to the coordination. The investigation by proton magnetic resonance spectroscopy in an aqueous solution gave more reliable information for the coordination of carboxyl group in penicillamine toward Hg
2+, Cd
2+ and Pb
2+.
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MASARU YAMAZAKI, NOBUHARU KAKEYA, TAKASHI MORISHITA, AKIRA KAMADA, MAS ...
1970 Volume 18 Issue 4 Pages
702-707
Published: April 25, 1970
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Based on the experimental observations that the concentrations of ionized and unionized molecules of sulfonamides at the bacteriostatis are linearly related to the drug's pK
a, equations of the relation of pK
a to bacteriostatic activity of sulfonamides against Escherichia coli are proposed. The optimal acid dissociation constant, pK
a0, of sulfonamides which are active at a minimum concentration is calculated. pK
a0 and the minimum bacteriostatic concentration are found to change with changes of pH of culture media.
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MASARU YAMAZAKI, NOBUHARU KAKEYA, TAKASHI MORISHITA, AKIRA KAMADA, MAS ...
1970 Volume 18 Issue 4 Pages
708-714
Published: April 25, 1970
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Hydrophobicity constant π, which was introduced by Hansch, of sulfonamides was measured in the systems of n-octyl alcohol-water (designated π
0) and chloroform-water (designated π
c). A good linear correlation was obtained between π
0 and π
c. π
c could be expressed in terms of log S
w, solubility of unionized molecules in water, and log S
c, solubility in chloroform. Binding of sulfonamides to human plasma protein, rabbit plasma and rabbit blood was measured following an equilibrium. dialysis method. A good correlation was obtained in any couple of the three measurements. The protein binding was found to be subjected to molecular weight of sulfonamides. Thus, an analysis was performed of the structure-activity relationship of sulfonamides between the bacteriostatic activity against Escherichia coli and the drug's physicochemical parameters including molecular weight.
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MILO GIBALDI, STUART FELDMAN, NORMAN D. WEINER
1970 Volume 18 Issue 4 Pages
715-723
Published: April 25, 1970
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The influence of a non-ionic surface active agent on the dissolution rate of benzoic and salicylic acids has been investigated and dissolution mechanisms have been examined as a function of the hydrodynamics of the system. Clearly, the dissolution rate of a solid in a micellar solution is not proportional to the solubility of the compound in the dissolution medium. Evaluation of dissolution rate data and theories has led to the conclusion that, depending upon hydrodynamic conditions, the dissolution rate of a solid will be proportional to the effective diffusion coefficient raised to a power between 0.5 and 1.0.
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KIICHIRO KAKEMI, HITOSHI SEZAKI, TAKAYOSHI MITSUNAGA, MASAHIRO NAKANO
1970 Volume 18 Issue 4 Pages
724-731
Published: April 25, 1970
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Salting behavior of alkylxanthines, other cyclic amides, and cyclic conjugated ketones was investigated by the solubility, partition, and permeation methods. These compounds were found to be salted-out by tetramethyl-and tetraethylammonium salts against the common belief that nonelectrolytes are salted-in by these salts. The above compounds were, however, salted-in by large ammonium salts and the effect was attributed to complex formation between the large ammonium ions and the nonelectrolytes. Salts were also shown to affect equilibrium concentrations of nonelectrolytes across a lipoid membrane and the rate of permeation of nonelectrolytes through the membrane.
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MICHIKO MIYAKI, BUNJI SHIMIZU
1970 Volume 18 Issue 4 Pages
732-740
Published: April 25, 1970
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The N-3→N-9 ribosyl (hydrogen halides or mercuric halides catalyzed) migration of N
6-acyl derivatives of 3-β-D-ribofuranosyladenine and its 5'-phosphate and 3-β-D-glucopyranosyladenine was found to occur by an intermolecular mechanism. Furthermore, formation of the 3-and 9-ribosyl derivatives was confirmed in the ribosylation reaction of N
6-benzoyladenine or its chloromercuri salt using milder conditions. These facts, contrary to the reports which described that the 9-glycosyl derivatives alone could be isolated, suggest that the reaction of N
6-benzoyladenine or its chloromercuri salt with glycosyl halides result in the initial formation of the 3-glycosyl derivatives followed by rapid conversion to the thermodynamically more stable 9-glycosyl derivatives in the presence of hydrogen halides or mercuric halides.
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MANKI KOMATSU, TSUYOSHI TOMIMORI, KATSUO HATAYAMA, YUKIKO MAKIGUCHI, N ...
1970 Volume 18 Issue 4 Pages
741-745
Published: April 25, 1970
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From the root of Sophora subprostrata CHUN et T. CHEN (Chinese drug : Shan Dou Gen ( ?? ?? ?? )) two new flavonoids, named sophoradochromene and sophoranochromene, have been isolated, whose structures have been established to be III and VII, respectively, by spectral and chemical data.
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YUKIO SUGIURA, HISASHI TANAKA
1970 Volume 18 Issue 4 Pages
746-751
Published: April 25, 1970
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Formation of new mixed ligand chelates consisting of penicillamine, bivalent metals, such as mercury, lead and cadmium, and some of the secondary ligands, such as mercaptoacetic acid, N-acetylpenicillamine, glutathione, 2-mercaptoethylamine, α-mercaptopropionyl glycine and penicillamine methyl ester, in the ratio of 1 : 1 : 1 were recognized potentiometrically, but there was no indication for the existence of the similar mixed ligand chelate in the cases of ethylmercaptan, glycine and histidine. The mixed ligand chelate is formed in two steps ; the simple penicillamine metal chelate is formed in the first step, and the secondary ligand becomes to coordinate to 1 : 1 penicillamine chelate to yield the 1 : 1 : 1 mixed ligand chelate in the second step. The order of the relative formation constants of mixed ligand chelates was Cd
2+>Hg
2+>Pb
2+. The formation constants of mixed ligand chelates are linearly correlated to the dissociation constants of sulfhydryl group in secondary ligands. Moreover, among these mixed ligand chelates, the decrease of binding affinity of the carboxyl group in penicillamine tends to increase the formation of the mixed ligand chelate.
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HIROSHI HIKINO, KUNIO AGATSUMA, CHOHACHI KONNO, TSUNEMATSU TAKEMOTO
1970 Volume 18 Issue 4 Pages
752-755
Published: April 25, 1970
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Two new furan-containing sesquiterpenoids, furanodiene and isofuranogermacrene (curzerene), have been isolated from zedoary, Curcuma zedoaria (Zingiberaceae), and shown by spectroscopic and chemical studies to have the structures I and II, respectively.
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YOSHINOBU GOTO, MOTOYOSHI YAMAZAKI
1970 Volume 18 Issue 4 Pages
756-762
Published: April 25, 1970
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The preparations of the so-called Reissert compounds of oxazole N-oxides were reported. Reactions of 2, 4, 5-tri-substituted oxazole N-oxides with potassium cyanide in the presence of benzoyl chloride afforded the Reissert compounds, i.e. N-benzoyloxy-2-cyano-4, 5-dimethyl-2-phenyl-(VII), 2-anisyl-N-benzoyloxy-2-cyano-4, 5-dimethyl-(XII), N-benzoyloxy-2-cyano-4-methyl-2, 5-diphenyl-(XIII) and 2-anisyl-N-benzoyloxy-2-cyano-5-methyl-4-phenyl-2, 3-dihydro-oxazole (XIV) respectively. The structures of these four compounds were determined by their chemical behavior and spectral data. Mass spectral data of VII, XII, XIII and XIV were recorded and discussed on their fragmentations.
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SABURO ISHIWATA, KEIICHI ITAKURA
1970 Volume 18 Issue 4 Pages
763-765
Published: April 25, 1970
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The Mannich reaction of 1-(3-amino)-and (3-amino-4-methoxy) benzyl-6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinolines (Va and Vb) with 36% formaldehyde solution in ethanol without acid afforded aminoprotoberberines (VIa and VIb), formed by cyclization at the position para to the amino group.
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AKIRA HANAKI
1970 Volume 18 Issue 4 Pages
766-770
Published: April 25, 1970
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The ionization constants of 2-aminoethylisothiuronium (AET) and 3-aminopropylisothiuronium (APT) salts, dibasic acid intrinsically, were determined potentiometrically. Those isothiuronium salts were extremely unstable and underwent the transguanylation, during the titration, through the conjugate base to the sulfhydryl compounds, which were ionized in the second step. For the determination of the ionization constant, the titration curve was treated as an equimolar mixture containing two acids. From the temperature dependence of the ionization constant, measured at 5°, 15°, 25° and 35°, was calculated the enthalpy of the ionization, which led to the evaluation of the entropy. The thermodynamic functions of those compounds at 25° were as follows : [table] The thermodynamic functions for the transguanylation and the cyclization products from those isothiuronium salts were also determined.
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MASAHIKO FUJINO, CHITOSHI HATANAKA, OSAMU NISHIMURA
1970 Volume 18 Issue 4 Pages
771-778
Published: April 25, 1970
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The synthesis of a tricosapeptide amide (α-
1-23NH2-ACTH) corresponding to the first 23-amino acid-sequence of corticotropin (ACTH) and β-alanine
1-α-
1-23NH2-ACTH is described. The carbobenzoxy group was used for the protection of the ε-amino function of the lysine residues and the nitro group was used for the protection of the guanido function of the arginine residues. Pentachlorophenyl trichloroacetate was successfully used for the synthesis of pentachlorophenyl active ester of the peptide fragments having c-terminal glycine and proline. Finally, all the protecting groups of the protected tricosapeptide amides were deblocked by the hydrogen fluoride method.
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AKIKO KANEMATSU, SHINSAKU NATORI
1970 Volume 18 Issue 4 Pages
779-783
Published: April 25, 1970
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The new triterpene carboxylic acid from 'fuling' was characterized as 3β-hydroxylanosta-7, 9 (11), 24-trien-21-oic acid (Ia) by the physical properties of the derivatives and by the derivation of Ia into dihydroagnosterol (VIa).
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MASUMI ITOH
1970 Volume 18 Issue 4 Pages
784-788
Published: April 25, 1970
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A facile procedure for the preparation of amino-protected amino acid activated ester was studied. Dimethylaryloxyformimidium chloride (V), which was easily prepared from aryl chloroformate (II) and dimethylformamide under the evolution of carbon dioxide, was allowed to react with amino-protected amino acids to give the corresponding activated aryl esters.
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HIROMICHI SAEKI, EIJI OHKI
1970 Volume 18 Issue 4 Pages
789-802
Published: April 25, 1970
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1, 2 : 3, 4-Di-O-isopropylidene-α-D-galacto-hexodialdo-1, 5-pyranose (4) was treated with sodium cyanide in aqueous methanol and the resulting cyanohydrin mixture (5a and 6a) was tosylated to give 1, 2 : 3, 4-di-O-isopropylidene-6-O-tosyl-L-glycero-(5b) and-D-glycero-α-D-galacto-heptopyranurononitrile (6b). Lithium aluminum hydride reduction of these tosylates 5b and 6b, followed by acetylation yielded D-glycero-N-acetylepimine (7a) and L-glycero-N-acetylepimine (8), respectively. The D-glycero-epimer (7a) thereby obtained was treated in warm acetic acid and gave a 6-acetamido-7-O-acetate (17a) exclusively, whose deacetylation with sodium methoxide yielded a 7-deacetyl derivative (19). Pfitzner-Moffatt oxidation of 19, followed by treatment of the resulting 7-oxo derivative (20) with methylmagnesium bromide gave 6-acetamido-6, 8-dideoxy-1, 2 : 3, 4-di-O-isopropylidene-L-threo-α-D-galacto-octopyranose (26). The latter (26) was converted into its D-erythro-derivative (24) by oxidation with chromium trioxide in pyridine and successive reduction with sodium borohydride. Hydrolysis of 24 with aqueous acetic acid or Amberlite IR-120 (H
+) gave the N-acetate of lincosamine which constitutes a sugar component of antibacterial antibiotic, lincomycin.
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MOTOHARU SHIBA, SUIICHI TOMIOKA, MASUMI KOISHI, TAMOTSU KONDO
1970 Volume 18 Issue 4 Pages
803-809
Published: April 25, 1970
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A study was made of the preparation of polyamide microcapsules containing aqueous bovine serum albumin solution. The size and size distribution were found to be independent of the concentration of bovine serum albumin. The formation of double microcapsules was frequently observed. Part of the amino residues of the encapsulated bovine serum albumin molecules was supposed to be chemically incorporated in the microcapsule membranes through the reaction with acid chloride.
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YOSHINARI HASEGAWA, TSUTOMU IRIKURA, DENICHI MIZUNO
1970 Volume 18 Issue 4 Pages
810-814
Published: April 25, 1970
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A screening of some substances for antimetastasis effect was carried out. The test system has previously been reported. The LP-12 line of Ehrlich ascites carcinoma cells were inoculated into the tail vein of ddY mice to give pulmonary tumor foci reproducively. Drugs to be tested were injected simultaneously with the tumor inoculation. Among some known antitumor drugs, bleomycin and cyclophosphamide have shown excellent effects. Non-ionic surface active agent, Triton X-100 also has been shown to give a slight activity.
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CHAUYANG CHEN, HARUHIKO YAMAMOTO, TAKAO KWAN
1970 Volume 18 Issue 4 Pages
815-819
Published: April 25, 1970
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Molecular forms of D-xylo-5-hexulosonate (5-keto-D-gluconate) in aqueous solutions were investigated by ultraviolet (UV), infrared (IR) and nuclear magnetic resonance (NMR), respectively, to see a reactive form that would participate in its catalytic hydrogenation by metals. Inspection of UV and IR spectra led to the result that both ketal and ketone forms coexist and that the two forms are readily convertible with each other. NMR spectra of 5-keto-D-gluconates were presented and discussed complementarily.
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SHUNICHI NAITO, KAZUO FUKUI
1970 Volume 18 Issue 4 Pages
820-823
Published: April 25, 1970
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YUKIKO TANAKA
1970 Volume 18 Issue 4 Pages
824-827
Published: April 25, 1970
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HIROSHI MITSUHASHI, KOJI HAYASHI, KOJI TOMIMOTO
1970 Volume 18 Issue 4 Pages
828-831
Published: April 25, 1970
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UKON NAGAI, MASATERU KURUMI
1970 Volume 18 Issue 4 Pages
831-834
Published: April 25, 1970
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KIICHIRO KAKEMI, HITOSHI SEZAKI, KIKUO IWAMOTO, HIROSHI KOBAYASHI
1970 Volume 18 Issue 4 Pages
834-838
Published: April 25, 1970
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MASAO SHIMIZU, OSAMU NAGASE, YASUHIRO HOSOKAWA, HIROAKI TAGAWA, YASUHI ...
1970 Volume 18 Issue 4 Pages
838-841
Published: April 25, 1970
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SHIGETAKA YOSHINA, ISAMU MAEBA
1970 Volume 18 Issue 4 Pages
842-847
Published: April 25, 1970
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HARUAKI YAJIMA, HIROKI KAWATANI, YOSHIAKI KISO
1970 Volume 18 Issue 4 Pages
850-851
Published: April 25, 1970
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HIROSHI HIKINO, YASUKO HIKINO, TSUNEMATSU TAKEMOTO, SHUJI TAKAHASHI
1970 Volume 18 Issue 4 Pages
852-854
Published: April 25, 1970
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MASAITI YASUE, TAKESHI KATO, JINSAKU SAKAKIBARA
1970 Volume 18 Issue 4 Pages
854-856
Published: April 25, 1970
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MASAITI YASUE, NORIHISA KAWAMURA, JINSAKU SAKAKIBARA
1970 Volume 18 Issue 4 Pages
856-858
Published: April 25, 1970
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AKIRA TAHARA, YASUO OHTSUKA
1970 Volume 18 Issue 4 Pages
859-860
Published: April 25, 1970
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YOSHIRO KOBAYASHI, ITSUMARO KUMADAKI, HARUO SATO
1970 Volume 18 Issue 4 Pages
861-862
Published: April 25, 1970
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MASAYOSHI OKIGAWA, TAKAKO MAEDA, NOBUSUKE KAWANO
1970 Volume 18 Issue 4 Pages
862-863
Published: April 25, 1970
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