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Volume 36, Issue 1
Displaying 1-9 of 9 articles from this issue
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Yoshio INAGAKI, Renji OKAZAKI1978 Volume 36 Issue 1 Pages 1-14
Published: January 01, 1978
Released on J-STAGE: January 22, 2010
JOURNAL FREE ACCESSEight thiocumulenes of the type X=S=Y (sulfur dioxide, disulfur monoxide, sulfur diimides, sulfinylamines, thiosulfinylamines, thiocarbonyl ylides, thiocarbonyl imines, and sulfines) were reviewed with respect to the structure, the preparation, and the reactivity (Diels-Alder type reaction, ene-reaction, photolysis, thermolysis, and reactions with nucleophiles, free radicals, carbenes, or nitrenes). Following relationships between the reactivity of the cumulene X=S=Y and the electronegativities (χX, χY) of the ligands (X, Y) were found : (1) the less are the values of χX+χY and |χX-χY|, the more is 1, 3-dipolar nature, rather than dienophilic nature, of the cumulene enhanced. (2) When χX>χY, the larger is the value of χX-χY, the more reactive is the S=Y bond. (3) Large value of χX+χY favors nucleophilic attack on to the central sulfur atom over the terminal atoms (X or Y).View full abstractDownload PDF (1608K) -
Yoshio ARATA, Miyoji HANAOKA1978 Volume 36 Issue 1 Pages 15-29
Published: January 01, 1978
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSConversion of bicyclic amines into medium-sized ring amines (tertiary and secondary) by selective cleavage of C-N or C-C bond is reviewed.
The effectiveness of 9a- or 8a-substituents on quinolizidines or indolizidines in the above conversion is described.View full abstractDownload PDF (1998K) -
Hideo KUROSAWA1978 Volume 36 Issue 1 Pages 30-40
Published: January 01, 1978
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSRecent developments in the study of model intermediates related to organic synthesis by means of palladium and platinum complexes are surveyed. Emphasis is placed on mechanistic aspects of some elementary steps fundamental to the synthetic reactions ; these include oxidative addition and reductive elimination reactions, and addition-elimination reaction of unsaturated compounds with metal complexes.View full abstractDownload PDF (1393K) -
Masato TANAKA1978 Volume 36 Issue 1 Pages 41-48
Published: January 01, 1978
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSPreparative methods of chiral phosphine ligands for catalytic asymmetric reactions were reviewed on the following items : 1. Preparation of P-chiral phosphines, 2. Preparation of C-chiral phosphines, 3. Determination of optical purity of P-chial phosphines.View full abstractDownload PDF (912K) -
Takeshi NAKAI1978 Volume 36 Issue 1 Pages 49-54
Published: January 01, 1978
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSRecent development in methodology for the nucleophilic introduction of the acetonyl functional group into organic substrates is surveyed. Scope and limitation for selected four reagents are described in some details.View full abstractDownload PDF (688K) -
Harumichi WATANABE1978 Volume 36 Issue 1 Pages 55-59
Published: January 01, 1978
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSFrom a modest beginning in the mid-1930's, the lubricating oil additive technology has become a major branch of the lubricating oil technology, with reported sales of more than 75, 000 tons annually in Japan. Additives of many diverse types have been developed to meet special lubrication needs such as, ring sticking of diesel engine, low temperature sludge of gasoline engine, corrosion of marine engine, long life oil for steam turbine, hypoid gear lubrication, severe oxidation problem of high temperature units, etc.View full abstractDownload PDF (911K) -
Hirotoshi HASEGAWA, Kenzi KONUMA, Kunio ITABASHI1978 Volume 36 Issue 1 Pages 60-64
Published: January 01, 1978
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSDuring the hydrogenolysis of octanethioic acid catalyzed by molybdenum trisulfide (MoS3) at 160300°C under the hydrogen pressure of 80 kg/cm2, 90 min, an appreciable amount of octyl octanethioate, octanoic acid, octanethiol and dioctyl sulfide were obtained as main intermediates. Especially, under the temperature below 200°C, the former two compounds were formed as the main products.
In order to elucidate the course of the reaction, octanethioic acid and related intermediates were subjeted to hydrogenolysis or heat-treatment under the various conditions. It was considered that octyl octanethioate might be produced by the reduction of dioctanoyl sulfide, and octanoic acid might be produced by the hydrolysis of octanethioic acid and or dioctanoyl sulfide. The whole reaction path for the formation of these main intermediates and final product are suggested.View full abstractDownload PDF (633K) -
Tsutomu KAMIYAMA, Masami INOUE, Saburo ENOMOTO1978 Volume 36 Issue 1 Pages 65-69
Published: January 01, 1978
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSThe catalytic hydrogenation of e-caprolactem to hexamethylenimine was carried out in a heterogeneous liquid phase reaction. Among the hydrogenation catalysts, Raney-Co showed an excellent activity and selectivity. The maximum yield of 88% was obtained with this catalyst at 190°C for 10 hrs in the medium of isoropylalcohol. At a higher temperature both the yield and the selectivity were decreased. In these cases, N-isopropyl hexamethylenimine and cyclohexanone were obtained as the by-products. The activity of Raney-Co was compared with those of Raney-Ni, Cu and Fe. With the Ni catalyst, the produced imine decomposed to yield piperidine and other undesirable by-products, while the Cu and Fe catalysts were almost inactive to the hydrogenation.
Also, δ-valerolactam and γ-butyrolactam were hydrogenated with Raney-Co catalyst in good yield.View full abstractDownload PDF (658K) -
Taketoshi KITO, Koki OTA, Yoshimi HARADA1978 Volume 36 Issue 1 Pages 70-71
Published: January 01, 1978
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSNaphtho [2, 1-b] furan was obtained in a good yield when alkali 2-naphthyl oxide or a mixture of 2-naphthol and alkali carbonate was heated in ethylene glycol monoalkyl ether at high temperatures in an autoclave. Although ethylene glycol monoacetate can be used in place of the monoalkyl ether, the yield was poor. The mechanism is being investigated.View full abstractDownload PDF (186K)
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