Journal of Japan Oil Chemists' Society
Online ISSN : 1884-2003
ISSN-L : 0513-398X
Volume 20, Issue 7
Displaying 1-10 of 10 articles from this issue
  • Teruzo ASAHARA, Manabu SENO, Sadayoshi TANAKA
    1971 Volume 20 Issue 7 Pages 385-394
    Published: July 20, 1971
    Released on J-STAGE: November 10, 2009
    JOURNAL FREE ACCESS
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  • Transition of Crystal Modification of 1-Monolaurin, 1-Monomyristin, 1-Monopalmitin and 1-Monostearin
    Takenori MARUYAMA, Isao NIIYA, Masao IMAMURA, Masakazu OKADA, Takeshi ...
    1971 Volume 20 Issue 7 Pages 395-402
    Published: July 20, 1971
    Released on J-STAGE: November 10, 2009
    JOURNAL FREE ACCESS
    1-Monolaurin, 1-monomyristin, 1-monopalmitin and 1-monostearin of over 99% in purity were synthesized and their polymorphic phenomena were examined by differential thermal analysis, and its results were compared with those from infrared absorption spectra and X-ray diffraction. Crystal modification was examined by polarization microscope and electron microscope with those having polymorphic crystals as confirmed by X-ray diffraction.
    1) Monoglycerides precipitated out very gradually from the solvent, showed only one melting peak and the peak temperature agreed with that of the β form in literature.
    2) Quenched sample showed variation in endothermic peak with increasing time of heat treatment, and endothermic corresponding to sub-α, α, β' and β were obtained.
    3) The time required for transition became faster in the order of monolaurin, monomyristin, monopalmitin and monostearin. Transition was detected earlier in the differential thermal analysis than by infrared absorption spectrum or X-ray diffraction, perhaps due to tempering effect during the measurement.
    4) T-T-T curve (transition curves) from (sub-α+α+β') to β form of monolaurin and monostearin showed a point of inflexion at 16°C and 31°C, respectively. Transition of (sub-α+α) to β' form of monopalmitin and monostearin also showed a point of inflexion, but in that of β' form to β form it indicated a fairly characteristic difference according to the number of carbon atoms.
    5) Reversible transition between sub-α and α form was confirmed even by differential thermal analysis by repeating cooling and heating.
    6) Results of observation through polarization microscope and electron microscope on four kinds of crystal modification confirmed by X-ray diffraction revealed that fine anisotropic crystal in sub-α grew into rhombic crystals on thermal stable state as transition progressed.
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  • Addition Reactions of Dimethyl Acetylenedicarboxylate to Methyl Conjugated Octadecadienoate
    Osamu SUZUKI
    1971 Volume 20 Issue 7 Pages 402-411
    Published: July 20, 1971
    Released on J-STAGE: November 10, 2009
    JOURNAL FREE ACCESS
    The Diels-Alder addition reactions of dimethyl acetylenedicarboxylate to methyl trans-9, trans-11- and cis-9, trans-11-octadecadienoate were studied. The kinetic study shows that the dimethyl acetylenedicaboxylate has about ten times as great dienophilic activity as methyl acrylate in the addition reaction to trans, trans-conjugated octadecadienoate.
    The adducts of dimethyl acetylenedicarboxylate to conjugated octadecadienoates were observed to have a 1, 4-cyclohexadiene structure by IR, NMR, and Mass spectral analyses. Furthermore, from the results of analysis of the reaction products, it has been found that the aromatization reaction of adducts proceeds along with the addition reactions.
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  • The Effect of Hydrogensulfide on the Reaction of Lauryl Chloride with Sodium Hydrogensulfide in n-Butanol
    Takeshi ARAI, Tsuneki SONODA, Motoo KOIKE
    1971 Volume 20 Issue 7 Pages 411-415
    Published: July 20, 1971
    Released on J-STAGE: November 10, 2009
    JOURNAL FREE ACCESS
    The effects of hydrogensulfide on the reaction of lauryl chloride (n-RCl) with sodium hydrogensulfide (NaSH) in n-butanol were mainly investigated. In the presence of hydrogensulfide, the yield of lauryl mercaptan increased remarkably and a side reaction (formation of sulfide : 2RCl+Na2S→RSR+2NaCl) was greatly decreased. From these results, it became clear that the following reaction mainly occurred :
    Na2S+H2S→2NaSH
    Moreover, the amount of water or n-butanol did not give much influence on the yield of mercaptan.
    In other experiments, the reactions of sec-RCl with NaSH were investigated. The reactivity of sec-RCl was lower by one half than that of n-RCl. But the reactivity of sec-RCl contained by several % in n-RCl was very low.
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  • Syntheses of Phenyl and Tolyl Derivatives
    Masahisa TAKASAGO, Kyo TAKAOKA, Manabu SENO
    1971 Volume 20 Issue 7 Pages 415-421
    Published: July 20, 1971
    Released on J-STAGE: November 10, 2009
    JOURNAL FREE ACCESS
    Thermal and photochemical syntheses of aryl derivatives with highly aliphatic chains were examined and the following results were obtained.
    1) The thermal reaction of decene-mercuric acetate adduct with benzene affords 1-phenyl-2-decene (yield 18.7%) as the main product, while the photochemical reaction affords 1-phenyl-1-decene (3.6%), 1-phenyl-2-decene (11.3%), 1-phenyl-3-decene (2.6%) and 1-phenyl-4-decene (1.6%).
    2) The thermal reaction of decene-mercuric acetate adduct with toluene affords 1- (2-methylphenyl) -2-decene (18.0%) and 1- (4-methyl-phenyl) -2-decene (23.5%) as main products, while the photochemical reaction gives 1- (3-methylphenyl) -decane (22.8%) and 1- (4-methylphenyl) -decane (31.3%).
    3) These products would be formed through heterolytic cleavage of aryl- (acetoxymercury) -decane with demercuration in the thermal process, while through homolytic cleavage in the photochemical process.
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  • Shigeyoshi MIYAGISHI, Shigetaka GOTO, Morie NISHIDA
    1971 Volume 20 Issue 7 Pages 422-424
    Published: July 20, 1971
    Released on J-STAGE: November 10, 2009
    JOURNAL FREE ACCESS
    An infrared method is reported in this paper for the quantitative determination of cationic surfactants with ammonium reineckate, NH4 [Cr (SCN) 4 (NH3) 2].
    Cationic surfactants were converted in to reineckates, which surfactant-reineckates were washed with water, and dried over phosphorus pentoxide. IR measurements of the reineckates were made by the pressed-disc technique. A strong absorption at about 1250cm-1 assigned to reinecke acid was used for their determinations, but each surfactant required each calibration curve.
    The determination of the mixed surfactants was also investigated.
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  • Isao MARUISHI, Shigeru TSUDA
    1971 Volume 20 Issue 7 Pages 425-433
    Published: July 20, 1971
    Released on J-STAGE: November 10, 2009
    JOURNAL FREE ACCESS
    Several polyoxyethylene alkyloylamide metal complexes were synthesized from two moles of polyoxyethylene alkyloylamide and one mole of calcium, nickel, zinc, and cupric chlorides; and of calcium, nickel, and cupric acetates.
    The effect of these metal complexes as internal antistatic agents for PVC was evaluated by measuring the frictional charge generation, induced charge decay and thermal stability.
    The antistatic effect of polyoxyethylene mono- and diethanolamide was great, and the improvement of the effect by metal complexing was less.
    Stearoyl derivatives were more effective than those having lauroyl group, and moles of ethylene oxide added showed little difference in 515 mole range.
    Generally, the metal complexes with low frictional charge generation showed low induced charge and fast charge decay.
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  • Sodium Salts of Organic Acids with the Alkyl Groups of about 8 Carbon Atoms
    Kazuo UMEHARA, Yoichi KATO
    1971 Volume 20 Issue 7 Pages 434-437
    Published: July 20, 1971
    Released on J-STAGE: November 10, 2009
    JOURNAL FREE ACCESS
    Compounds with alkyl chain length of about 8 carbon atoms that contained mainly organophosphorus compounds were prepared and the inhibitive properties were examined by various corrosion tests. The organophosphorus compounds had less inhibitive effect in water-rich circumstance, but they had more inhibitive effect in lean-water circumstance. It was determined that corrosion product obtained in aqueous solution of sodium n-octylphosphate was ferric salt of n-octylphosphoric acid. The compounds used here except glycine derivative possess fairly good inhibitive properties.
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  • Setsuko ENDO, Yasue YOSHIOKA, Tatsuo MITSUHASHI
    1971 Volume 20 Issue 7 Pages 437-439
    Published: July 20, 1971
    Released on J-STAGE: November 10, 2009
    JOURNAL FREE ACCESS
    The lipids of Hirafusube and Ohchirimentake were investigated on their general properties, the fatty acid compositions determined by GLC, and the characteristics of unsaponifiable matters.
    The lipids were obtained by extracting the dried matters with ether, then treated with n-hexane. The general properties of the lipids were as follows; Hirafusube (d254 0.9486, n25D 14800, I.V. 91.5, A.V. 29.6, S.V. 156.0); Ohchirimentake (I.V. 77.2, A.V. 17.1).
    The fatty acid compositions of Hirafusube were C10 : 0 0.2, C10 : 1 (?) 0.3, C12 : 0 1.6, C14 : 0 1.6, C14 : 1 (?) 0.9, C16 : 0 11.5, C16 : 1 (?) 0.6, C16 : 2 (?) 2.0, C18 : 0 3.1, C18 : 1 45.6, C18 : 2 28.3, C18 : 3 (?) 1.0, C20 : 0 2.1, C20 : 1 (?) 1.2 and those of Ohchirimentake were C10 : 0 1.1, C10 : 1 (?) 0.7, C12 : 0 2.7, C14 : 0 3.2, C14 : 1 (?) 3.8, C16 : 0 15.3, C16 : 1 (?) 6.8, C18 : 0 7.1, C18 : 1 20.5, C18 : 2 35.6, C18 : 3 (?) 2.2, C20 : 0 1.0.
    The main sterols in the unsaponifiable matters of Hirafusube and Ohchirimentake were both considered to be ergosterol and fungisterol from the data of melting points, IR and UV adsorption spectra, and GLC of the sterols and their acetates.
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  • Ayao KITAHARA
    1971 Volume 20 Issue 7 Pages 440-446
    Published: July 20, 1971
    Released on J-STAGE: November 10, 2009
    JOURNAL FREE ACCESS
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