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HARUO SAIKACHI, HARU OGAWA, KATUTOSHI SATO
1969 Volume 17 Issue 9 Pages
1757-1766
Published: September 25, 1969
Released on J-STAGE: March 31, 2008
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Preparation of aryl 2, 4-dialkyl-2, 4-pentadienals (aryl is (5-nitro-2-furyl)- or (5-nitro-2-thienyl)-, alkyl is methyl or ethyl) by condensation of alkyl enol ether R-CH=CH-OR R〓H) with aryl-α-alkylated acrolein acetals gave stereoselectively 2-cis-4-trans-2, 4-dialkylated pentadienals. Driving force leading to above configuration is overcrawding control of the sterically hindered chain. The stereoselective formation of cis-alkenals was found to be applicable for aryl 2-cis-4-cis-6-trans-trialkylated heptatrienal. All hindered cis alkenals prepared in this paper cyclized to five or seven membered cyclic ketones in the presence of HCl or some organic acids. A mechanism for the cyclization was proposed, that involves initial formation of oxocarbonium ion, which is later transformed by two of successive processes, i.e., the formation of bicyclo-[2.1.0] cyclopentanone derivative and its ring rupture by acid. Proposed mechanism was discussed from the result of deuterohydrochloric acid incorporated cyclization of IVa.
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ZENZO TAMURA, YOICHI IITAKA, YASUMASA KIDO
1969 Volume 17 Issue 9 Pages
1767-1770
Published: September 25, 1969
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The crystal structure of the colored substance in the Millon reaction of p-cresol, a complex consisting of 2-mercuri-4-methylphenol and 2-nitroso-4-methylphenol, was determined by the single crystal X-ray diffraction method. The complex purified from chloroform crystallizes in triclinic crystal system, space group Pl, with each two molecules of the complex, C
14H
12O
3NHg, and chloroform in a cell dimensions a=10.6Å, b=15.0Å, c=5.6Å, α=95°30', β=94°20', γ=100°30'. As the three-dimensional refinement of the crystal structure has not been attempted, valency angles and bond lengths are not clear, but the probable structure of this complex has been discussed from the result of the final two-dimensional refinement.
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KENJI FUKUZAWA, YASUO SUZUKI, MITSURU UCHIYAMA
1969 Volume 17 Issue 9 Pages
1771-1777
Published: September 25, 1969
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1) The effect of tocopheronolactone on two lipid-peroxidation systems, one is the enzymatic system coupled to NADPH oxidation and stimulated by ADP-Fe
+2 mixture (NADPH-ADP-Fe
+2 system), and the other is non-enzymatic system induced by ascorbate and Fe
+2 (ascorbate-Fe
+2 system), were studied. 2) The quinol form of tocopheronolactone inhibited the autoxidation of unsaturated fatty acid, but quinoid form of it, unlike ubiquinone and p-benzoquinone, did not show the antioxidant activity. 3) The enzymatic reduction of tocopheronolactone was inhibited by dicoumarol which peculiarly inhibit the quinone reductase. 4) Though antioxidant activity of tocopheronolactone on the ascorbate-Fe
+2 lipidperoxidation system come into effect through the prior reduction to quinol, its activity on the NADPH-ADP-Fe
+2 lipid-peroxidation system seems to be caused by intact quinone. Such assumption could be introduced by taking the effect of dicoumarol on above two system into consideration. 5) Tocopheronolactone did not inhibit the NADPH-linked metabolism of aminopyrine and codeine.
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YOSHIO SASAKI, MIYOKO SUZUKI
1969 Volume 17 Issue 9 Pages
1778-1781
Published: September 25, 1969
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Meta
1H and
13C chemical shifts of monosubstituted benzene and pyridine derivatives have been correlated with respect to the substituent constants σ
i and σ
π, and following results are presented. a) The π-electronic contributions observed among both
1H and
13C shifts are positive. b) Above conclusions are also reliable in substituted pyridines.
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TOSHIO NAMBARA, KYOKO YAMANOUCHI, YOSHIKO KOBAYASHI
1969 Volume 17 Issue 9 Pages
1782-1786
Published: September 25, 1969
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Requirements of the configuration at C-14 and C-13 for the aromatization of C
19 steroids by human placenta have been investigated. For this puropose 14β-and 13α-androst-4-en-3-ones were synthesized as the substrate (see Chart 2). The C/D-cis-linked steroids as well as androsta-4, 14-diene-3, 17-dione were transformed into the 17-hydroxylated estrogens, when incubated with the placental 10000×g supernatant in the presence of NADPH and oxygen. The relative yield of Kober chromogens produced from these C
19 steroids was found to be lower than that of androst-4-ene-3, 17-dione having normal C/D-ring juncture as listed in Table I.
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TAKAKO TOMITA, TATSUO OZAWA, ISAO TOMITA
1969 Volume 17 Issue 9 Pages
1787-1793
Published: September 25, 1969
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1. The effects of carbon sources on growth, acetoin formation, respiration and fermentation of Saccharomyces carlsbergensis were examined in relation with myo-inositol (m-I) deficiency. Among five fermentable sugars tested (glucose, galactose, fructose, sucrose and mannose) galactose was unique in receiving very little effect of m-I deficiency ; no growth depression, much less O
2 uptake inhibition and almost negligible accumulation of acetoin. A cyclization of galactose to m-I without conversion to glucose is suggested. 2. There existed a close correlation between the inhibition of growth or O
2 uptake and acetoin formation, namely the larger the inhibition of growth or respiration the higher the acetoin accumulation took place. RD mutant of Saccharomyces carlsbergensis, however, did not produce much acetoin in the absence of m-I. m-I deficiency thus seems to be manifested when the respirative activities are repressed. 3. The effect of carbon sources on m-I deficiency of the yeast were also reproducible with cell suspensions prepared from the yeast grown on each sugar mentioned above. Pyruvate could also be used as substrate though the formation of acetoin was less.
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SHUNICHI NAITO, MITSUO MIZUTANI, KAZUHIKO KITAO, SACHIKO NISHIMURA
1969 Volume 17 Issue 9 Pages
1794-1798
Published: September 25, 1969
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Metabolites of guaiacol glycerol ether and its mononicotinate in rabbit urine were investigated. As the metabolites of guaiacol glycerol ether, β-(2-methoxyphenoxy) lactic acid, (2-methoxyphenoxy) acetic acid, β-(4-hydroxy-2-methoxyphenoxy) lactic acid, and (4-hydroxy-2-methoxyphenoxy) acetic acid (trace) were separated with unchanged GGE, and identified with the authentic samples by thin-layer chromatography. Two of the metabolites, β-(4-hydroxy-2-methoxyphenoxy) lactic acid and (4-hydroxy-2-methoxyphenoxy) acetic acid showed hypocholesteremic action on hypercholesteremia caused by intravenous injection of Triton to rats. As metabolites of guaiacol glycerol ether in rabbit liver and kidney in vitro, only β-(2-methoxyphenoxy) lactic acid was detected with the unchanged drug by thin-layer chromatography.
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YOSHIO SASAKI, MIYOKO SUZUKI
1969 Volume 17 Issue 9 Pages
1799-1808
Published: September 25, 1969
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π-Electron charge density distributions from both corrected ring
1H chemical shift and modified Hueckel Molecular Orbital Method-ω Technique-have been compared in 3-and 4-pyridines, 6-quinolines and 6-quinoxalines. The plots of above two kinds of charge density distributions against substituent constant σ
π showed similar gradients with each other, but relative intersections are unsatisfactory.
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TETSUJI KAMETANI, MASUO KOIZUMI, KEIICHIRO FUKUMOTO
1969 Volume 17 Issue 9 Pages
1809-1814
Published: September 25, 1969
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The thermal decomposition of the diazonium salt, derived from 1-(2-amino-3, 4, 5-trimethoxybenzyl) -1, 2, 3, 4-tetrahydro-6, 7-dimethoxy-2-methylisoquinoline (XI) which was prepared by an usual method, by our method gave the morphinandienone type compound (C-nor-androcymbine) (X). This paper also described the approaches to the synthesis of androcymbine (I).
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MAMORU KAMIYA
1969 Volume 17 Issue 9 Pages
1815-1820
Published: September 25, 1969
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A five-spin iterative analysis was performed for the nuclear magnetic resonance spectrum of the benzoxazole protons. The converged values of the coupling constants showed that the long-range couplings between the oxazole ring proton and the other protons were supported by the McConnell's theory on the π-electron coupling in aromatic molecules using molecular orbital method, and the analyses for all combinations of the signs of the two prominent long-range coupling constants indicated that these were of the same sign. There was no distinct correlation between the chemical shifts of the protons and the calculated π-electron densities.
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MAMORU KAMIYA, SEIJI KATAYAMA, YUKIO AKAHORI
1969 Volume 17 Issue 9 Pages
1821-1826
Published: September 25, 1969
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The NMR spectra of the benzenoid ring protons in benzoxadiazole, benzothiadiazole, benzoselenadiazole and quinoxaline have been analyzed as AA'BB' spin systems by an iterative method. The theoretical spectra showed good agreements with the experimental spectra in line frequencies and their relative intensities. The obtained chemical shifts and coupling constants exhibit some interesting features corresponding to the molecular structural changes arised from the replacement of oxygen by sulfur, selenium and carbon double bond. The chemical shift ν
Oδ
AB was found to decrease with the more delocalized π-electron distribution and to suggest a d-orbital model for sulfur. The relative magnitudes of the two ortho-coupling constants and their variations from molecule to molecule were tentatively correlated with the changes of the internal bond angles in the benzenoid ring. The relation of J
para>J
meta in benzoxadiazole was interpreted in terms of a negative contribution of π-electrons to J
meta.
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SADAO NISHIGAKI, FUMIO YONEDA, KAZUKO OGIWARA, TAKEO NAITO, RENZO DOHM ...
1969 Volume 17 Issue 9 Pages
1827-1831
Published: September 25, 1969
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In order to test of antimicrobial activity, 1-ethyl-1, 4-dihydro-7-[2-(5-nitro-2-furyl)-vinyl]-4-oxo-1, 8-naphthyridine-3-carboxylic acid (V) which contained nalidixic acid and 5-nitro-2-furaldehyde was prepared and a convenient method for the synthesis of its derivatives was studied.
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RENZO DOHMORI, SHIZUO KADOYA, YOSHIAKI TANAKA, ISAO TAKAMURA, RYUICHI ...
1969 Volume 17 Issue 9 Pages
1832-1838
Published: September 25, 1969
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For screening of antimicrobial agent, a series of 1-substituted 1, 4-dihydro-7-[2-(5-nitro-2-furyl) vinyl]-4-oxo-1, 8-naphthyridine-3-carboxylic acids was synthesized and some of these compounds were converted to the corresponding esters and amides via the acid chloride.
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AKIRA HANAKI
1969 Volume 17 Issue 9 Pages
1839-1846
Published: September 25, 1969
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Copper-catalyzed oxidation of ascorbic acid was investigated in various environments by using the conventional Warburg manometric technique. The rate of the oxidation, expressed by the consumption of molecular oxygen, depends on pH and the concentration of ascorbic acid. From the pH dependence of the reaction, it was deduced that the dissociated monoionic ascorbic acid was a molecular species susceptible to the oxidation. Inorganic ligand including buffer anion influenced the oxidation. Nitrate, sulfate and acetate ions, which have a little ability to complex with copper ion, reduce a little the catalytic efficiency. The retardation by acetate ion was ascribed to the formation of copper tetraacetate. Halide, pyrophosphate, thiocyanate and cyanide ions, which complex preferably with cuprous ion thereby change the redox potential between cupric and cuprous ions, retards the oxidation markedly.
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KAORU ABE, MASAYUKI ONDA, SHIGENOBU OKUDA
1969 Volume 17 Issue 9 Pages
1847-1853
Published: September 25, 1969
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Sodium borohydride reduction of 14β-bromocodeinone was reexamined using deuterated reagents, and the position deuterated and deuterium contents of labeled products were measured by nuclear magnetic resonance and mass spectrometer to confirm the reaction routes and quantitative relationship of each of these routes, and reaction mechanisms were proposed.
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MAMORU KAMIYA
1969 Volume 17 Issue 9 Pages
1854-1863
Published: September 25, 1969
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The NMR spectra of ortho haloanilines measured in various solvents were analyzed as ABCD spin systems and the proton chemical shifts and spin-spin coupling constants were determined. Upon these data, solvent effects on the internal chemical shifts were investigated. The main feature in the solvent effects was the selective deshielding of the proton ortho to the amino substituent in polar solvents. The above shift in polar solvents was explained by a specific solute-solvent association involving a hydrogen-bonding formation which was competitive with the intramolecular interaction between the substituents and a polar mesomeric structure of the solute molecule was also considered for the explanation of the variation of the other internal chemical shifts. Furthermore, the solvent shifts in inert solvents and toluene were discussed. The proton chemical shifts of the isolated molecules were found to have large departures from those predicted by the additivity rule.
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KIICHIRO KAKEMI, HITOSHI SEZAKI, TAKASHI KONDO
1969 Volume 17 Issue 9 Pages
1864-1870
Published: September 25, 1969
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The gastrointestinal absorption of pyridine aldoxime methiodides has been studied in rats using single loop and perfusion techniques. Contrary to their apparent physicochemical properties, these compounds were absorbed from the intestine to an appreciable extent but not from the stomach and the rectum within one hour. The absorption from the intestine became saturated when the concentration of the drugs increased and one will inhibit the absorption of the other. The presence of a metabolic inhibitor in the drug solution had no effect on the absorption of these compounds. Despite the complexity of the systems used, a straight line relationship between the reciprocal of absorption rate and the reciprocal of initial concentration was obtained for each compound studied.
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MICHIO MATSUI, TOKIO KAIZU, MASASHI OKADA, MORIZO ISHIDATE
1969 Volume 17 Issue 9 Pages
1871-1877
Published: September 25, 1969
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Serum D-glucaric acid (V) level was determined by the colorimetric method, especially after oral administration of D-glucuronolactone (I) or D-glucarolactones (II, III) to man. The highest level was observed at one hour after administration simultaneously with the lowest level of serum β-glucuronidase activity as well as the maximal β-glucuronidase inhibition of serum. In vivo conversion of I into β-glucuronidase inhibitor was thus demonstrated.
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ZENICHI HORII, KAZUO OHKAWA, SANGWON KIM, TAKEFUMI MOMOSE
1969 Volume 17 Issue 9 Pages
1878-1882
Published: September 25, 1969
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1-Hydroxy-3-hydroxymethyl-6, 7-dimethoxy-4-(3, 4-methylenedioxyphenyl)-2-naphthoic acid γ-lactone (II) was synthesized from 3, 4-dimethoxy-3', 4'-methylenedioxybenzhydrylidenesuccinic acid (III) by an unambiguous 10-step procedure shown in Chart 1, and was found not to be identical with diphyllin. A revised structure (XII) was proposed to diphyllin by assuming an intermolecular hydrogen bonding to its characteristic lactone carbonyl band of extreme low frequency, 1709 cm
-1 (Nujol), in the IR spectrum.
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TADAHIKO OTAKA, MITSURU UCHIYAMA
1969 Volume 17 Issue 9 Pages
1883-1888
Published: September 25, 1969
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The administration of ecdysterone to mice is accompanied by the incorporation of orotic acid into ribonucleic acids in the liver. This effect was completely repressed by actinomycin D. Judging from the template activity of RNA in an amino acid-incorporating system and the results of sucrose gradient analysis, it is obvious that the rate of synthesis of messenger RNA is regulated by ecdysterone as well as other RNA in mouse liver. The stimulating effect of ecdysterone on protein synthesis reported previously can be explained at least partially in terms of its influence on messenger RNA synthesis.
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TETSUZO KATO, HIROSHI YAMANAKA, JUNSHI KAWAMATA, HIROMI SHIMOMURA
1969 Volume 17 Issue 9 Pages
1889-1895
Published: September 25, 1969
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The reaction of β-aminocrotonamide (V) with ketene afforded α-acetyl-β-aminocrotonamide (VII). When the reaction was carried out in the presence of triethylamine or pyridine, α-acetyl-β-acetylaminocrotonamide (VIII) was obtained. Heating of the diacetyl compound (VIII) with sodium hydroxide gave 5-acetyl-2, 6-dimethyl-4 (1H)-pyrimidone (IX) in good yield. Similarly, the reaction of β-amino-N-methylcrotonamide (XII) with ketene afforded α-acetyl-β-acetylamino-N-methylcrotonamide (XV) and 5-acetyl-2, 3, 6-trimethyl-4 (1H)-pyrimidone (XIV). On the other hand, the treatment of β-amino-N, N-dimethylcrotonamide (XIII) with ketene resulted in the formation of a resinous product. The reaction of V or XII with diketene yielded 3-acetyl-4-hydroxy-6-methyl-2 (1H)-pyridone derivatives. The reaction of XIII with diketene gave only nitrogen free compounds.
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SHINICHI KONDO, KENJI KAWAMURA, JUNKO IWANAGA, MASA HAMADA, TAKAAKI AO ...
1969 Volume 17 Issue 9 Pages
1896-1901
Published: September 25, 1969
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Leupeptins which have anti-plasmin activity and inhibit trypsin, papain and blood coagulation have been obtained from cultured broths of various species of Actinomycetes. Two leupeptins which were leupeptins Pr (C
21H
40O
4N
6) and Ac (C
20H
38O
4N
6) were isolated and characterized. They gave their di-n-butyl acetals, dihydroleupeptins and leupeptin acids. Physical and chemical properties of these leupeptins and their derivatives were described.
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KENJI KAWAMURA, SHINICHI KONDO, KENJI MAEDA, HAMAO UMEZAWA
1969 Volume 17 Issue 9 Pages
1902-1909
Published: September 25, 1969
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The structures of two major components, leupeptins Pr-LL and Ac-LL, isolated from cultures of various species of Actinomycetes, have been investigated. Mild acid hydrolysis of leupeptins Pr-LL and Ac-LL gave propionyl-and acetyl-L-leucyl-L-leucine, whose structures were established by syntheses. Complete acid hydrolysis of leupeptin acids derived by oxidation of leupeptins gave L-leucine and DL-arginine. The structures of leupeptins Pr-LL and Ac-LL were determined to be propionyl- and acetyl-L-leucyl-L-leucyl-DL-argininal, respectively, and confirmed by the syntheses. Propionyl-and acetyl-L-leucyl-L-leucyl-L-arginine methyl esters were reduced to their alcohols with lithium borohydride and then oxidized to respective leupeptins Pr-LL and Ac-LL by sulfoxidecarbodiimide reaction.
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YOSHIHIRO NISHIKAWA, TADAHIRO TAKEDA, SHOJI SHIBATA, FUMIKO FUKUOKA
1969 Volume 17 Issue 9 Pages
1910-1916
Published: September 25, 1969
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The acyl group attached to the antitumor active polysaccharide (GE-3) isolated from G. esculenta has been identified as O-acetyl, and the content was determined to be about 2%. The O-acetyl groups were located in the 3-position of the glucose units by employing the method of Bouveng. The molecular weight of the polysaccharide was calculated to be approximately 20000 by equilibrium ultracentrifugation. The antitumor effects of some derivatives of GE-3 were tested against the implanted sarcoma-180. The results suggested that the O-acetyl groups are concerned in the antitumor activity. The identity of the polysaccharide isolated from L. papulosa with GE-3 has been further extended, since the acyl group attached to the former was also proved to be O-acetyl.
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KAORU ABE, YUMIKO NAKAMURA, MASAYUKI ONDA, SHIGENOBU OKUDA
1969 Volume 17 Issue 9 Pages
1917-1923
Published: September 25, 1969
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Solvolysis of indolinocodeine derivatives (III and IV) was carried out under the conditions employed for conversion of morphine series compounds into indolinocodeine series compounds to attempt their conversion to morphine type skeleton, and VI was obtained from III. An assumed mechanism through an aziridinium intermediate was proposed.
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AKIRA TAKAMIZAWA, KENTARO HIRAI
1969 Volume 17 Issue 9 Pages
1924-1930
Published: September 25, 1969
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A convenient method for the preparation of 4-p-substituted phenyl-1, 3-dithiolium salts was presented. 4-p-Substituted phenacyl N, N-dialkylaminocarbodithioates easily obtained from the reaction of N, N-dialkylamine N, N-dialkylaminocarbodithioates and p-substituted phenacylbromides were cyclized to give 2-immonium 1, 3-dithiole salts. Reduction of immonium salts was performed by the action of NaBH
4 to give 2-amino-1, 3-dithiole and the action of acid to this amine gave 1, 3-dithiolium salts immediately. The yield of each step was very high and the operation was simple, giving pure 1, 3-dithiolium salts. The properties of intermediates and 4-p-substituted phenyl-1, 3-dithiolium salts were described.
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AKIRA TAKAMIZAWA, KENTARO HIRAI
1969 Volume 17 Issue 9 Pages
1931-1936
Published: September 25, 1969
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Nucleophilic reagents attacked exclusively to C-2 position of 4-phenyl-1, 3-dithiolium cation derivatives and the corresponding 1, 3-dithioles were obtained in good yields. Thus, 2-amino-, 2-aminothiocarbonylthio-, 2-phenylthio-1, 3-dithioles were yielded. LiAIH
4 reduction furnished 1, 3-dithiole and hydride abstraction gave original cation. 1, 3-Dithiolium cation acted as a Bronsted acid and conjugate base carbinol was isolated. Similarly, covalent 2-alkoxy compounds were easily obtained and regenerated cation by the action of acid. Grignard reaction toward cation opened the new routes to 2-substituted 1, 3-dithiolium cations.
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MASAHIKO FUJINO, OSAMU NISHIMURA
1969 Volume 17 Issue 9 Pages
1937-1941
Published: September 25, 1969
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A number of esters of carbobenzoxyamino acids with acetoxime, cyclopentanonoxime and cyclohexanonoxime have been synthesized by direct condensation using dicyclohexylcarbodiimide. These esters are stable and crystalline solids (including carbobenzoxy-serine, -threonine and-nitroarginine) and react readily with amino acid esters or peptide esters in the presence of acid catalyst such as acetic acid, formic acid or phenylacetic acid. Because of the easy availability and the water solubility of the simple ketoximes, these active esters should be useful for the peptide synthesis.
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HIROYUKI INOUYE, SHUJI INOUYE, NORIAKI SHIMOKAWA, MASAYOSHI OKIGAWA
1969 Volume 17 Issue 9 Pages
1942-1948
Published: September 25, 1969
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Four new glucosides, paederoside (II), paederosidic acid (III), scandoside (IV) and deacetylasperuloside (V) along with asperuloside (I) were isolated as iridoid glucosides from Paederia scandens (LOUR.) MERRILL var. mairei (Leville) HARA and their structures were established. II and III are sulfur-containing glucosides. III and V seem to be the artefacts formed during the extraction process.
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HIROYUKI INOUYE, MASAYOSHI OKIGAWA, NORIAKI SHIMOKAWA
1969 Volume 17 Issue 9 Pages
1949-1954
Published: September 25, 1969
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Prolonged boiling of an aqueous solution of asperuloside (I) afforded scandoside (III), deacetylasperuloside (V), deacetylasperulosidic acid (IX), 10-acetylascandoside (X), and asperulosidic acid (XI). A methanolic solution of I gave deacetylasperuloside (V) and daphylloside (XII) on the same treatment. Prolonged boiling of an aqueous solution of paederoside (II) gave paederosidic acid (IV) and 6-epipaederosidic acid (XIII). Deacetylasperuloside (V) and paederosidic acid methyl ester (VI) were obtained by boiling a methanolic solution of II.
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MASATAKA ICHIKAWA, HISASHI ICHIBAGASE
1969 Volume 17 Issue 9 Pages
1955-1958
Published: September 25, 1969
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HARUAKI YAJIMA, NARIAKIRA MIZOKAMI, YOSHIO OKADA, KOICHI KAWASAKI
1969 Volume 17 Issue 9 Pages
1958-1962
Published: September 25, 1969
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HARUAKI YAJIMA, YOSHIAKI KISO
1969 Volume 17 Issue 9 Pages
1962-1964
Published: September 25, 1969
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AKIRA HANAKI
1969 Volume 17 Issue 9 Pages
1964-1966
Published: September 25, 1969
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TOSHIO IMANARI, YASUAKI ARAKAWA, ZENZO TAMURA
1969 Volume 17 Issue 9 Pages
1967-1969
Published: September 25, 1969
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TSUNEMATSU TAKEMOTO, TORU OKUYAMA, SHIGENOBU ARIHARA, YASUKO HIKINO, H ...
1969 Volume 17 Issue 9 Pages
1973-1974
Published: September 25, 1969
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HIROMICHI SAEKI, EIJI OHKI
1969 Volume 17 Issue 9 Pages
1974-1976
Published: September 25, 1969
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