Journal of Synthetic Organic Chemistry, Japan
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
Volume 36, Issue 12
Displaying 1-16 of 16 articles from this issue
  • Addition of Amino Acids to Nucleic Acids
    Isao SMTO, Satoru ITO
    1978 Volume 36 Issue 12 Pages 1009-1022
    Published: December 01, 1978
    Released on J-STAGE: November 13, 2009
    JOURNAL FREE ACCESS
    Photochemical reactions of pyrimidine and purine bases are reviewed. These include photodimerization, photohydration, and photoadditions of pyrimidine bases. Photoadditions of nucleic acid with a wide variety of compounds are also described. In particular, photoinduced addition of amino acids to nucleic acid constituents are discussed in connection with the photoinduced cross-linking of nucleic acids to proteins.
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  • Yasuyuki SHIMOHIGASHI, Nobuo IZUMIYA
    1978 Volume 36 Issue 12 Pages 1023-1038
    Published: December 01, 1978
    Released on J-STAGE: November 13, 2009
    JOURNAL FREE ACCESS
    Natural dehydroamino acids and dehydropeptides are reviewed with respect to the isolation, the structure, and the biological activities. Synthetic aspects on dehydropeptides are also reviewed, and finally, the structure and function of AM-toxins, phytotoxic cyclotetradepsipeptides containing a dehydroalanine, are discussed through synthetic studies.
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  • Tetsuya UCHINO
    1978 Volume 36 Issue 12 Pages 1039-1044
    Published: December 01, 1978
    Released on J-STAGE: November 13, 2009
    JOURNAL FREE ACCESS
    The recent trends of fluoro-organic specialty chemical industry were reviewed.
    The market, general information and application of water and oil repellent, surfactans, lubricants biomedical chemicals were included.
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  • Manzo ITO
    1978 Volume 36 Issue 12 Pages 1045-1049
    Published: December 01, 1978
    Released on J-STAGE: November 13, 2009
    JOURNAL FREE ACCESS
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  • [in Japanese], [in Japanese]
    1978 Volume 36 Issue 12 Pages 1050
    Published: December 01, 1978
    Released on J-STAGE: November 13, 2009
    JOURNAL FREE ACCESS
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  • Kenzi KONUMA, Hirotoshi HASEGAWA, Kunio ITABASHI
    1978 Volume 36 Issue 12 Pages 1051-1057
    Published: December 01, 1978
    Released on J-STAGE: November 13, 2009
    JOURNAL FREE ACCESS
    In the hydrogenolysis of thiobenzoic acid catalyzed by molybdenum trisulfide (MoS3) at 160280°C under the hydrogen pressure of 80 kg/cm2, 90 min, toluene and dibenzyl were obtained at final products. During the course of the reaction, appreciable amount of S-benzyl benzothioate and benzoic acid were obtained as main intermediates, whereas α-toluenethiol and didenzyl sulfides were scarcely obtained as intermediates.
    In order to elucidate the course of the reaction, the related intermediates of thiobenzoic acid were synthesized, and these hydrogenolyses or heat-treatment were carried under the various conditions. It was considered that S-benzyl benzothioate might be produced by the reduction of dibenzoyl sulfide, and benzoic acid might be produced by the hydrolysis of thiobenzoic acid and/or dibenzoyl sulfide. It was presumed that dibenzoyl sulfide might be produced by dehydrogensulfurization of thiobenzoic acid and partially by desulfurization of dibenzoyl disulfide which might be produced by dehydrogenation of thiobenzoic acid.
    The whole reaction path for the hydrogenolysis of thiobenzoic acid are suggested.
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  • Kunio ITO, Shingo MIYAJIMA, Kazunori NAKABAYASHI
    1978 Volume 36 Issue 12 Pages 1058-1063
    Published: December 01, 1978
    Released on J-STAGE: November 13, 2009
    JOURNAL FREE ACCESS
    The Michael addition of N- (2, 2-dialkylethylidene) -t -butylamines to methyl vinyl ketone took place smoothly to produce 5, 5-dialkyl-6- (t-butylimino) -2-hexanones in 8997 % yields.
    Treatment of the adducts with equimolar amount of hydrochloric acid afforded 2, 2-dialkyl-5-oxhexanals in 8393 % yields, while treatment with excess hydrochloric acid gave 4, 4-dialkyl-2-cyclohexen-1-ones in 8297 % yields. In the case of the imines derived from dialkylacetaldehydes and straight chain amines, the Michael addition, was accompanied by ring formation, leading to the mixtures of N- (4, 4-dialkyl-2-cyclohexenylidene) alkylamines and 4, 4-dialkyl-2-cyclohexen-1-ones. N-Propylidene- and N-butylidene-t-butylamine gave 5-methyl- and 5-ethyl-5- (t-butyliminomethyl) -2, 8-nonanedione, which on treatment with equimolar amount of hydrochloric acid gave the corresponding aldehydes.
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  • Giichi SAITO, Kanji SATO, Nobuo ABE
    1978 Volume 36 Issue 12 Pages 1064-1067
    Published: December 01, 1978
    Released on J-STAGE: November 13, 2009
    JOURNAL FREE ACCESS
    Methylcyclopentenes, which are useful intermediates for the synthesis of five membered alicyclic compounds, were prepared by means of thermal isomerization of cyclohexene over natural zeolite (clinoptilolite type) at 430440°C in good yield (cf. Table 1). Similarly, cyclohexanol was dehydrated and isomerized directly over zeolite at 430 °C to yield 1-and 3-methylcyclopentenes (cf. Table 2).
    The zeolite was quite active in these reactions. It was also active in establishing equilibrium between these hydrocarbons which are differing only in the position of a double bond. The ratio of 1-and 3-methylcyclopentenes was always about 73 : 27 under these reaction conditions (cf. Table 3). The isomerized methylcyclopentenes were converted to the corresponding trans glycols by oxidation with hydrogen peroxide in formic acid.
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  • Studies on the Oxidation of Toluic Acids in Molten Potassium Hydroxide. I
    Hideo UEHARA, Michinori OKI
    1978 Volume 36 Issue 12 Pages 1068-1072
    Published: December 01, 1978
    Released on J-STAGE: November 13, 2009
    JOURNAL FREE ACCESS
    A new oxidation system of toluic acids which is performed in molten potassium hydroxide (1) with manganese dioxide (2) has been studied. Terephthalic acid was obtained in 87mol% yield from p-toluic acid (3), under the condition of molar ratio (2) / (3) 3.0, weight ratio (1) / (3) 8, reaction temperature 275 °C and reaction time 1 hr. Isophthalic acid was obtained in 57 mol % yield from m-toluic acid (4) under the condition of molar ratio (2) / (4) 3.0, weight ratio (1) / (4) 8, reaction temperature 200°C and reaction time 2 hr. Phthalic acid was obtained in 52 mol % yield from o-toluic acid (5) under the condition of molar ratio (2) / (5) 3.0, weight ratio (1) / (5) 8, reaction temperature 250°C and reaction time 1 hr.
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  • Studies on the Oxidation of Toluic Acids in Molten Potassium Hydroxide. II
    Hideo UEHARA, Michinori OKI
    1978 Volume 36 Issue 12 Pages 1073-1078
    Published: December 01, 1978
    Released on J-STAGE: November 13, 2009
    JOURNAL FREE ACCESS
    The oxidizing action of the new oxidizing system using molten potassium hydroxide-manganese dioxide-air was studied.
    In the reaction in nitrogen, the mean oxidation number of the recovered manganese was 2.90, and the yield of terephthalic acid (1) was 33 mol %. The result is explainable by the decrease of the oxidation number of manganese from 4 mostly to 3 and partly to 2.
    In the reactions in air and oxygen, the oxidation numbers of the recovered manganese were 3.68 and 3.73, and the yields of (1) were 87 and 76 mol %. In these cases the results are not explainable only by the decrease of the oxidation state of manganese.
    Further, it was found that potassium manganate (MnVI) is partly formed in molten KOH-MnO2 in air at the reaction temperature of about 250°C.
    From these facts, it has become clear that the manganese in molten KOH-MnO2 in air may function as oxidizing agents with the oxidation number between 6 and 2, and may behave as a catalyst catching oxygen from the atmosphere and giving it to organic compound.
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  • Studies on the Oxidation of Toluic Acids in Molten Potassium Hydroxide. III
    Hideo UEHARA, Michinori OKI
    1978 Volume 36 Issue 12 Pages 1079-1084
    Published: December 01, 1978
    Released on J-STAGE: November 13, 2009
    JOURNAL FREE ACCESS
    The oxidation of p-toluic acid in molten potassium hydroxide was studied with various metal oxides under an normal pressure of air. It was found that p-toluic acid is oxidized to terephthalic acid with silver (I) oxide, vanadium (V) oxide, iron (III) oxide, mercury (II) oxide, molybdenum (VI) oxide, cobalt (III) oxide, thallium (III) oxide, copper (II) oxide, copper (I) oxide and potassium chromate.
    The oxidation is mainly performed with the decrease of the oxidation number of the metals in the potassium salts of metallic acids which are formed from metal oxides dissolving in molten potassium hydroxide.
    A higher yield of terephthalic acid was obtained by the use of the metal compound in higher oxidation state. In general, terephthalic acid was formed in higher yield with a metal compound of smaller standard oxidation reduction potential (EOB) in alkaline medium such as MnO42-→MnO2, Ag2O→Ag and PbO2→PbO.
    From this general rule one can expect what substance is effective in this oxidation process. As an example, oxygen (EOB = -0.401 volt) can be used under an initial pressure of 30 kg/cm2 to give terephthalic acid in 83 mol % yield from p-toluic acid. Thus it can be used as a new oxidation method of organic compounds.
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  • Tsunehiro YAMASHITA, Itsuki OKUDA, Hironari SUGIYAMA
    1978 Volume 36 Issue 12 Pages 1085-1089
    Published: December 01, 1978
    Released on J-STAGE: November 13, 2009
    JOURNAL FREE ACCESS
    Arsenic (III) dithiocarbamates were synthesized by the reaction of diarsenic trioxide with secondary amine and carbon disulfide.
    Various dialkylamines and cyclic amines gave the dithiocarbamates in excellent Yield, but monoalkylamines gave the resinous matter.
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  • Itsuki OKUDA, Hironari SUGIYAMA
    1978 Volume 36 Issue 12 Pages 1090-1094
    Published: December 01, 1978
    Released on J-STAGE: November 13, 2009
    JOURNAL FREE ACCESS
    Alkyl isothiocyanates were obtained in favorable yield by the reaction of diarsenic trioxide with monoalkylamine and carbon disulfide in molar ratio 1 : 3 : 3. When lead (II) oxide instead of diarsenic trioxide was used in this reaction, lead (II) dithiocarbonimidates were formed in high yield, which on standing or on heating gave pure isothiocyanates. Further, it was found that alkyl isothiocyanates were formed in good yield by the reaction of triethylammonium dithiocarbonimidate with arsenic trichloride. From these results, a new mechanism for the formation of alkyl isothiocyanates in the present process was proposed.
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  • Toshiyuki TANAKA, Tokuyuki KURODA
    1978 Volume 36 Issue 12 Pages 1095-1100
    Published: December 01, 1978
    Released on J-STAGE: November 13, 2009
    JOURNAL FREE ACCESS
    The oxidation of 2, 2-bis (hydroxymethyl) propionaldehyde (HMPAL) to 2, 2-bis (hydroxyme thyl) propionic acid (HMPA) with oxygen was studied.
    Higher acid value than the calculated value base on HMPAL and formation of HMPA in decent yield were observed upon irradiation of HMPAL in ethyl acetate with UV light in a stream of oxygen. The oxidation was assumed to proceed co-oxidatively with a peroxy acid derived from the oxidative decomposition of ethyl acetate.
    Isobutyraldehyde was effective as a co-oxidizing reagent in the oxidation of HMPAL with oxygen, but acetaldehyde showed no effect. The effectiveness of isobutyraldehyde was assumed to its structural suitability.
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  • Kunio ITO, Satoshi NAGAI, Shingo MIYAJIMA
    1978 Volume 36 Issue 12 Pages 1101-1103
    Published: December 01, 1978
    Released on J-STAGE: November 13, 2009
    JOURNAL FREE ACCESS
    Partial hydrogenation of diphenylacetylenes to stilbenes was effected with high selectivity by hydrogen transfer from N-benzylaniline in the presence of palladium-charcoal. 1, 3-, 1, 5-Cyclooctadiene, and trans, trans, trans-1, 5, 9-cyclododecatriene were hydrogenated selectively to the corresponding monoenes.
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  • Use of Cyclopentadiene IV
    Koji ISOGAI, Takashi SASAKI, Chizuko SATO
    1978 Volume 36 Issue 12 Pages 1104-1109
    Published: December 01, 1978
    Released on J-STAGE: November 13, 2009
    JOURNAL FREE ACCESS
    The Beckmann fission of 2-acetoxycyclopentanone oxime (1e) and 2-benzoyloxycyclopentanone oxime (1f) with phosphorus pentachloride at 0°C gave5-acetoxy-5-chlorovaleronitrile (3e) and 5-benzoyloxy-5-chlorovaleronitrile (3f) in 56 %and 71 % yields, respectively. The hydrolysis of (3e) gave 4-cyanobutanal (2) and 5-acetoxy-cis-4-pentenenitrile (5). The methanolysis of (3e) gave (2) and its dimethyl acetal (6). These reactions proceeded by the Sn1 mechanism. The reaction of (3e) with several nucleophiles were carried out in anhydrous and aqueous solvents. Sodium cyanide and silver nitrite reacted with (3e) in anhydrous tetrahydrofuran or diethyl ether to give 2- acetoxyadiponitrile (7) (99 ro) and 1-acetoxy-4-cyanobutyl nitrite (9) (59 %), respectively. Sodium azide and sodium acetate hardly reacted with the chlorine of (3e) in anhydrous acetone, whereas 5-acetoxy-5-azidovaleronitrile (10) and 5, 5-diacetoxyvaleronitrile (11) were obtained in about 20 % yield in aqueous acetone.
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