YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
Volume 84, Issue 9
Displaying 1-24 of 24 articles from this issue
  • Den'ichi Mizuno
    1964 Volume 84 Issue 9 Pages 787-792
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
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  • Synthesis and Antimicrobial Activity of 3-(5-Nitro-2-furyl) acryl-Heterocyclic Compounds
    Tsutomu Irikura, Kazunari Shirai, Shimao Sato
    1964 Volume 84 Issue 9 Pages 793-796
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
    In a search for new antibacterial agents, combination of nitrofuran ring and heterocycle was attempted and over 10 kinds of new derivatives were prepared. An antifungal compound, S-(1-oxido-2-pyridyl)-5-nitro-2-furanthioacrylate, was found by antifungal tests using Trichophyton.
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  • Syntheses of 1-Phenyl-2 (or 3)-aminoalkanethiol Derivatives
    Haruki Nishimura, Hideji Takamatsu
    1964 Volume 84 Issue 9 Pages 797-805
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
    Various derivatives (II) of 1-phenyl-2-aminoethanol were obtained by the application of an amine to 2-bromoacetophenone followed by reduction, or by amination of 1-phenyl-2-bromoethanol, and chlorination of II afforded the corresponding 2-chloro-2-phenylethylamine derivatives (III). Application of sodium hydrosulfide, sodium thiosulfate, or thiourea to III gave the corresponding thiosulfonic acid (IV) or isothiuronium salt (V), and treatment of IV with hydrochloric acid or of V with alkali produced 1-phenyl-2-aminoethanethiol derivatives (VI), which were oxidized to the corresponding disulfides (VII). VI was also obtained by the amination of α, β-epithiostyrene (VIII), while desulfurization of IV with Raney nickel gave 2-phenylethylamine derivatives. These experiments proved that the reaction of III to IV and V was not accompanied by rearrangement-substitution. 1-Phenyl-3-alkylaminopropanethiol and its disulfide were synthesized from 1-phenyl-3-alkylaminopropanol in a similar manner.
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  • Configuration of 1-Phenyl-2-alkylaminopropanethiol. (1)
    Haruki Nishimura
    1964 Volume 84 Issue 9 Pages 806-811
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
    From the strength of the hydrogen bonding between N and SH in the infrared absorption spectra of (+)- and (-)-1-phenyl-2-dimethylaminopropanethiol (III and III′), obtained by the application of sodium thiosulfate to L-(+)-threo- and L-(-)-erythro-N, N-dimethyl-1-chloro-1-phenyl-2-propylamine hydrochlorides (I and I′), followed by hydrolysis, it was assumed that III is the threo series and III′, the erythro series. III is also obtained by the application of potassium thioacetate or sodium hydrosulfide to I or by application of thiourea followed by alkali treatment of the isothiuronium salt (V) thereby formed.
    Similarly, two kinds of 1-phenyl-2-methylaminopropanethiol (VIII and VIII′) and 2-imino-3, 4-dimethyl-5-phenylthiazolidine (X and X′), derived from L-(+)-threo- and L-(-)-erythro-N-methyl-1-chloro-1-phenyl-2-propylamine hydrochloride (VI and VI′) by the application of foregoing reagents, were also determined of their steric configuration in relation to III and III′. These experiments proved that application of nucleophilic reagents to I, I′, VI, and VI′ afforded derivatives without change in their steric configuration.
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  • Configuration of 1-Phenyl-2-alkylaminopropanethiol. (2). Hofmann Degradation of 1-Phenyl-2-dimethylaminopropanethiol Quaternary Salt
    Haruki Nishimura
    1964 Volume 84 Issue 9 Pages 811-817
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
    Application of sodium thiosulfate to L-(+)-threo-N, N-dimethyl-1-chloro-1-phenyl-2-propylamine hydrochloride, followed by hydrolysis gave (+)-1-phenyl-2-dimethylaminopropanethiol (II) which was derived to the quaternary salt (IV or V) and treated with sodium hydroxide to form (+)-1, 2-epithiopropylbenzene (VI′). Treatment of D-(+)-erythro-1, 2-epoxypropylbenzene (VIII′) with potassium thiocyanate gave L-(-)-erythro-1, 2-epithiopropylbenzene (IX′), which was found to be the antipode of VI′. It is therefore assumed that VI′ is the D-(+)-erythro series and II, the L-(+)-threo series.
    (-)-Aminothiol (II′), similarly derived from L-(-)-erythro-N, N-dimethyl-1-chloro-1-phenyl-2-propylamine hydrochloride (I′) was found to be the L-(-)-erythro series and that D-(+)-threo-epithio compound (VI) is derived from it. Steric configuration of VI and VI′ was also determined from their nuclear magnetic resonance spectra. Hofmann degradation of the quaternary salt of 1-phenyl-2-dimethylaminoethanethiol also gave the same result. Epithio compounds (VI and VI′) underwent desulfurization by heating and produced trans-β-methylstyrene.
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  • Configurations of N-Alkyl-1-phenyl-2-chloropropylamines and their Rearrangements with Nucleophilic Reagents
    Haruki Nishimura
    1964 Volume 84 Issue 9 Pages 817-824
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
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    Treatment of DL-erythro-1-methylamino-1-phenyl-2-propanol (V) hydrochloride with phosphorus pentachloride or with thionyl chloride results in the formation of two kinds of N-methyl-1-phenyl-2-chloropropylamine hydrochloride (VI and VI′). Application of sodium thiosulfate to VI and VI′ gave the thiosulfonic acid derivatives (VII and VII′). VII′ obtained from VI′ was found to be DL-threo-1-phenyl-2-methylaminopropylthiosulfonic acid, and VII obtained from VI was found to be the erythro compound formed by rearrangement. This result indicates that this reaction proceeds with two Walden inversions via the intermediate aziridinium compound. Actually, treatment of VI and VI′ with sodium hydroxide respectively afforded DL-threo- and DL-erythro-1, 2-dimethyl-3-phenylaziridine (XVIII′ and XVIII). This fact shows that VI is the erythro series and VI′, the threo series. Application of hydrosulfide or thioacetate to VI and VI′ gave the expected rearrangement products.
    The only product, N, N-dimethyl-1-phenyl-2-chloropropylamine hydrochloride (XX), obtained by chlorination of DL-1-dimethylamino-1-phenyl-2-propanol, also afforded the rearranged erythro compound by application of similar nucleophilic reagents and XX was found to be the erythro series compound.
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  • Rearrangements of 1-Phenyl-2-chloroethylamines with Nucleophilic Reagents
    Haruki Nishimura
    1964 Volume 84 Issue 9 Pages 824-830
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
    Application of nucleophilic reagents, such as alkoxides, sodium hydroxide, sodium thiosulfate, and sodium hydrosulfide, to DL- and D-N, N-dimethyl-1-phenyl-2-chloroethylamine (VI and XIV) gave DL- and L-N, N-dimethyl-1-phenyl-1-(substituted)ethylamines. This reaction showed that there is apparently a steric correlation between the starting. compounds and the products. The same reaction of 1-phenyl-2-chloroethylamine by the application of sodium thiosulfate or sodium hydrosulfide gave the rearrangement products, 1-phenyl-2-aminoethylthiosulfonic acid and 1-phenyl-2-aminoethanethiol. VI and XIV were found to undergo facile rearrangement by heating to DL- and L-N, N-dimethyl-2-chloro-2-phenylethylamines. Based on these results, steric configuration of the optically active N, N-dimethyl-2-chloro(mercapto-, substituted mercapto-, or alkoxy)-2-phenylethylamines was determined.
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  • Shoji Toyoshima, Satoru Tanaka, Tatsuo Komaki
    1964 Volume 84 Issue 9 Pages 830-836
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
    1-Arylsulfonyl-2, 3-dialkyl-2-thiopseudoureas (VI) were synthesized via 1, 2-dialkyl-2-thiopseudoureas (V) according to the method of Winthrop, and the properties of these V and VI are given in Tables I and II. VI, similar to sulfonylthioureas, undergo desulfurization by silver salt, iron salt, and chromium trioxide to form the corresponding 1-arylsulfonyl-3-alkylureas (VII). Desulfurization of 1-(p-acetylbenzenesulfonyl)-2-benzyl-3-cyclohexyl-2-thiopseudourea (VI-32), symthesized via p-acetylbenzenesulfonyl chloride (XII) which obtained by oxidation of p-ethylbenzenesulfonyl chloride (XI) with chromium trioxide, affords 1-(p-acetylbenzenesulfonyl)-3-cyclohexylurea (VII-3) but chromium trioxide oxidation of 1-(p-ethylbenzenesulfonyl)-2-benzyl-3-cyclohexyl-2-thiopseudourea (VI-37) gives VII-3 in one step. Under a mild oxidation condition, 1-(p-ethylbenzenesulfonyl)-3-cyclohexylurea (VII-4) is formed.
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  • Color Reaction of Phenols with 1-Nitroso-2-naphthol
    Masuo Umeda
    1964 Volume 84 Issue 9 Pages 836-838
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
    Coloration of phenols with 1-nitroso-2-naphthol in nitric acid solution was examined. About fifty phenolic compounds were examined and the specificity of para-substituted phenols to this coloration reported to date does not seem to be necessarily true. This coloration reaction occurs with all phenols having a positive substituent and those with negative substituent hardly undergo this coloration. Specificity of 1-nitroso-2-naphthol to para-substituted phenols is observed only when the concentration of this reagent is low. This is probably due to the fact that para-substituted phenols easily undergo nitration with nitric acid and form nitrophenols which do not react with 1-nitroso-2-naphthol. The same coloration occurs with 2-nitroso-1-naphthol and disodium 3-hydroxy-4-nitroso-2, 7-naphthalenedisulfonate, but less readily than with 1-nitroso-2-naphthol. The same coloration reaction was also found to occur with the use of ammonium cerium sulfate in place of nitric acid.
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  • On the Mechanism of Color Reaction of p-Substituted Phenols with 1-Nitroso-2-naphthol and Nitric Acid
    Masuo Umeda
    1964 Volume 84 Issue 9 Pages 839-845
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
    Examinations were made on the mechanism of coloration reaction of para-substituted phenols with 1-nitroso-2-naphthol·nitric acid. The structure of the reaction product was clarified and the mechanism was elucidated. p-Cresol, 2-naphthol, and 4′-hydroxy-acetanilide were used as the para-substituted phenol, they were colored by 1-nitroso-2-naphthol in nitric acidity, and extract of the colored solution with ethyl acetate was chromatographed over alumina column. The product thereby obtained were 10-methyl-5H-benzo [a] phenoxazin-5-one (I) from p-cresol, 5H-dibenzo [a, j]-phenoxazin-5-one (II) from 2-naphthol, and 10-acetamido-5H-benzo [a] phenoxazin-5-one (III) from 4′-hydroxy-acetanilide. Besides III, 10-acetamidobenzo [a] phenoxazonium nitrate (IV) was also obtained, which is responsible for coloration and easily converted to III in an aqueous solution. It is assumed from these evidences that, in this coloration reaction, condensation of para-substituted phenols with 1-nitroso-2-naphthol in nitric acidity takes place first to form labile benzo [a] phenoxazonium nitrate with coloration, and this compound further undergoes oxidation to form the 5H-benzo [a] phenoxazin-5-one derivatives.
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  • Colorimetric Determination of Resorcinol with 1-Nitroso-2-naphthol and Nitric Acid, and its Reaction Mechanism
    Masuo Umeda
    1964 Volume 84 Issue 9 Pages 846-851
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
    Colorimetric determination of resorcinol with 1-nitroso-2-naphthol in nitric acid solution was established and its reaction mechanism was clarified. Reaction of resorcinol and 1-nitroso-2-naphthol in the presence of nitric acid and a minute quantity of sodium nitrite produces reddish violet color which has absorption maximum at 550mμ. This colored solution was diluted with a large volume of water, extracted with chloroform, and the product was purified by silica column chromatography. The product was found to be 9H-benzo [a] phenoxazin-9-one, agreeing with the compound synthesized by another route. It was assumed that this product, formed via an indophenol compound, colors reddish violet on being dissolved in nitric acid. For the colorimetric determination of resorcinol, the following method is recommended.
    One ml. of the sample solution (containing 10-120γ/ml. of resorcinol) is accurately measured into a 10ml. flask, 1ml. of 0.1% 1-nitroso-2-naphthol solution, 1ml. of 0.05% sodium nitrite solution, and 1ml. of 2.5N nitric acid are added. The mixture is shaken well and allowed to stand at 50° for 15 minutes. The flask is immersed in an ice bath and the cooled content is brought exactly to 10ml. with ethanol. Absorbancy of the solution is measured at 550mμ. A blank test is carried ont with the same amount of the same reagent, using 1ml. of water in place of the sample solution. Accuracy of this method is σ=1.36% (n=6).
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  • Relation between Apparent Dielectric Constant of Compressed Tablet and Contained Water
    Isamu Horikoshi, Hajime Sano
    1964 Volume 84 Issue 9 Pages 851-856
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
    Solid pharmaceutics were made into tablets by high-pressure, tabletting and apparent dielectric constant and dielectric loss of the tablets were measured. This made it possible to know the difference in the binding of the substrate and water. When water is contained as the water of crystallization, apparent dielectric constant is in the range of 2 to 5, and when present as adsorbed water, as is the case in high molecules, the value was found to become large.
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  • Temperature Dependence of Dielectric Properties and Pyrolysis of Hydrated Crystals
    Isamu Horikoshi, Ikuzo Himuro, Hajime Sano
    1964 Volume 84 Issue 9 Pages 856-861
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
    Apparent dielectric constant and dielectric loss of hydrates in accordance with temperature changes were measured and by comparison of these values with weight changes as measured by thermobalance, nature of water in hydrates was examined in detail. This method was found to make simple discrimination of water of crystallization, sorbed water, and free water. The method also enables measurement of melting and decomposition points.
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  • Influence of Anions for Crystallization
    Masayuki Nakagaki, Tadao Fujie
    1964 Volume 84 Issue 9 Pages 861-869
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
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    Effect of anions on the synthesis of crystalline aluminosilicates was studied in connection with the hitherto reported fact that aluminum chloride can be used instead of sodium aluminate as the aluminum source.
    Anions such as C1-, NO3-, CO32-, SO42-, PO43-, SCN-, and I- were used and their effect was examined by using solutions instead of suspensions, since hydrothermal reaction was effected by the use of sodium aluminate solution as the aluminum source, and silica solution as the silicon source.
    When silica/alumina ratio n is large and alkali is present in excess of above 300%, species P instead of species R was likely to be produced in the presence of anions, especially of PO43-, in the solution. When n<1, species Q was formed.
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  • Reaction of Picolines and their N-Oxides with Methyl Iodide or Benzyl Chloride
    Tetsuzo Kato, Yoshinobu Goto, Manabu Hikichi, Takeshi Kawamata
    1964 Volume 84 Issue 9 Pages 869-873
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
    α-Picoline 1-oxide undergoes reaction with benzyl chloride in liquid ammonia, in the presence of potassium amide, to form 2-dibenzylmethylpyridine 1-oxide in far larger amounts than phenethylpyridine 1-oxide. This fact indicates that the methyl group had been activated by the presence of N-oxide, compared to the reaction of α-picoline reported by Bergstrom and others.
    Reaction of three kinds of picoline and their N-oxides with methyl iodide indicated that the methyl group is activated by the N-oxide group, that β-methyl group has less reactivity, and that the ease of alkylation decreases in the order of γ, α, β in the case of picolines and in the decreasing order of α, γ, β in picoline 1-oxides.
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  • Syntheses of Wollenberg Type Compounds and Studies on their Structures by Infrared Absorption Spectra
    Tetsuzo Kato, Tsunehiro Kitagawa
    1964 Volume 84 Issue 9 Pages 874-879
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
    Isoquinoline, lepidine, and methyl isonicotinate react with diketene to form Wollenberg-type compounds (III, IV, and V). These compounds form dehydro derivatives by dehydrogenation. Hydrolysis of the dehydro compound of III affords compounds with the γ-pyrone ring opened. The ultraviolet absorption spectra of these compounds endorsed these reactions. Examination of their infrared absorption spectra indicated that the Wollenberg-type compounds previously reported, including pyridine-diketene adduct (I) and quinoline-diketene adduct (II), take the a-type structure.
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  • Analysis of Alkylpyridine Derivatives
    Bunpei Negishi, Keishiro Nishi
    1964 Volume 84 Issue 9 Pages 879-883
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
    Analysis of alkylpyridines in dry distillate of non-fat soybean was examined. Analysis by infrared spectra of the fractional distillate was almost identical with the result of direct analysis of the component by gas chromatography. Twelve alkylpyridines were thus identified.
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  • Tatsu Kawano, Masako Asakawa
    1964 Volume 84 Issue 9 Pages 884-886
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
    Decarboxylase activity of 12 kinds of microorganisms on 21 kinds of amino acid was examined by paper electrophoresis. It was thereby found that Escherichia coli No.1 effected decarboxylation of arginine, glutamic acid, lysine, ornithine, histidine, aspartic acid, and canavanine, E. coli K12 that of arginine, glutamic acid, lysine, ornithine, histidine, tyrosine, aspartic acid, and canavanine, Streptococcus faecalis ATCC-8043 that of tyrosine, Proteus vulgaris HX 19 and Lactobacillus arabinosus 17-5 that of glutamic acid, Lact. fermenti 36 that of glutamic acid and histidine, Aerobacter aerogenes No.3059 and Proteus morganii No.3168 that of glutamic acid and ornithine, and Clostridium welchii SR 12 that of glutamic and aspartic acids.
    Carbon dioxide formed by decarboxylation of glutamic acid by Lact. arabinosus 17-5 was approximately 90% of the calculated amount in 1 hour so that this cannot be used for the determination of glutamic acid.
    Microbiological determination of the decarboxylatlon product of aspartic acid by E. coli No.1 showed that the amount of α-alanine formed is only about 1% of the calculated and the main decarboxylation product is assumed to be β-alanine.
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  • The Constituents of the Bark of Firmiana platanifolia SCHOTT et ENDL
    Yoshihisa Tanabe, Kiyo Ogura, Shigenori Sakai, Kotaro Takahashi
    1964 Volume 84 Issue 9 Pages 887-889
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
    Lupenone, octacosanol, and sucrose were isolated from the bark of Firmiana platanifolia SCHOTT et ENDL.
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  • Synthesis of 5-Nitrofurfural N-Substituted Aminoacylhydrazone Derivatives and Related Compounds
    Akio Fujita, Shinsaku Minami, Hideji Takamatsu
    1964 Volume 84 Issue 9 Pages 890-893
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
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    In order to test their antibacterial activity N-substituted aminoacylhydrazone, N-(substituted phenylsulfonyl)aminoacylhydrazone, and N-(substituted phenyl)carbamoylacetyl-hydrazone derivatives of 5-nitrofurfural (I) and 5-nitro-2-furanacrolein (II) were synthesized.
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  • Masakazu Aritomi, Kuniko Miyazaki, Tatsuji Mazaki
    1964 Volume 84 Issue 9 Pages 894-895
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
    Presence of quercitrin was proved in the leaves of Rhus javanicus L. (Anacardiaceae), and of rutin and kaempherol 3-L-rhamno-D-glucoside in the leaves of Melia Azedarach var. subtripinnata MIQUEL (Meliaceae).
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  • Masakazu Aritomi, Michiko Shimojo, Tatsuji Mazaki
    1964 Volume 84 Issue 9 Pages 895-896
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
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    A flavonoid glycoside, C21H20O11⋅3H2O, m.p. 168-178°, was isolated in a pure state from the flowers of Gnaphalium affine D. DON (Compositae), and identified as luteolin 4′-β-D-glucoside.
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  • Syntheses of 1-Substituted 3-Dimethylamino-1, 2, 3, 4-tetrahydroquinoline Derivatives
    Isao Satoda, Fuyuki Kusuda, Yoshiharu Matsuo, Nobukiyo Tatewaki
    1964 Volume 84 Issue 9 Pages 897-899
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
    As part of attempts to find new antipyretic-analgesic agents, following the previous work on the syntheses of quinoline and cinchophen derivatives, derivatives of 1-acyl-3-dimethylamino-1, 2, 3, 4-tetrahydroquinoline and its related compounds were synthesized. Some examinations were made on their synthetic methods and some of its observations are reported.
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  • Minoru Tohda, Noriaki Kuwana, Kiyoshi Kawabe
    1964 Volume 84 Issue 9 Pages 900-904
    Published: September 25, 1964
    Released on J-STAGE: February 19, 2010
    JOURNAL FREE ACCESS
    Morpholinoacetohydrazide (I) and 4-hydrazinoformylmethyl-4-methylmorpholinium halide (II) were found to have the capacity to separate effectively the two components from a mixture of 4-en-3-one and 1, 4-dien-3-one steroids in a pure state. I and II had the property of selectively binding with 4-en-3-one steroid and their selectivity was equal to that of the Girard reagent. The hydrazone formed with II is water-soluble and separation of the unreacted 1, 4-dien-3-one steroid becomes easy. Actual application of these compounds effected recovery of each component in a high yield from a mixture of these steroids. II is less hygroscopic than the Girard reagent.
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