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Volume 35, Issue 2
Displaying 1-7 of 7 articles from this issue
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Properties in the Nonadjacent n, π Interacting SystemsKenichi YOSHIKAWA, Isao MORISHIMA1977 Volume 35 Issue 2 Pages 83-93
Published: February 01, 1977
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSAuthors' recent studies concerning the structural effects on the lone pair orientation and electronic state of N-heterocyclic molecules were reviewed. Especially, nonadjacent n, π interacting systems were studied in relation to homoallyl and bishomoallyl interactions. It was concluded that n and π electrons are repulsive in bishomoallyl and bishomobenzyl n, π interacting systems, while these electrons are electronically rather attractive in homoallyl and homobenzyl interacting systems, and that the lone pair electrons prefer the orientation in which the interacting system is more stabilized. Along with these studies, various physico-chemical properties of N-heterocyclic compounds were discussed, i.e., 1H and 13C nmr paramagnetic shifts, magnetic anisotropic effect of lone pair electrons, basicities and ionization potentials.View full abstractDownload PDF (1632K) -
Jiro TSUJI1977 Volume 35 Issue 2 Pages 94-108
Published: February 01, 1977
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSVarious synthetic reactions catalyzed by palladium complexes are classified and explained by typical examples. These reactions include carbonylation, decarbonylation, dimerization of butadiene and isoprene, addition of allene, exchange of allylic and vinylic compounds, addition of olefins, displacement of organic halides, reactions of acetylenes, silanes, and amines.View full abstractDownload PDF (1743K) -
Junji FURUKAWA1977 Volume 35 Issue 2 Pages 109-115
Published: February 01, 1977
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSIn the homopolymerization of butadiene, the control of cis, trans and vinyl structure of the polymer was achieved by the nickel catalyst with various electron-donor and electron-acceptor. The author proposed so-called back-biting coordination as a general mechanism for the control of the structure, in which the double bond of the penultimate unit can coordinate to nickel facilitating cis-polymeization and the addition of co-catalyst affects the mode of bidentate of unidentate coordination of butadiene monomer.
The copolymerization of diene and monoolefin was succeeded by controlling the available coordination site for bidentate coordination of diene and unidentate coordination of monoolefin. In this way, the alternating copolymer of butadiene and propylene was prepared as an excellent synthetic rubber.
The control of mode of dimerization of butadiene was also achieved with zero-valent nickel added by protic compounds with a contorolled strength and a proper amount. In this way, the coupling of butadiene is controlled through proton-transfer or intermolecular insertion reaction. This sort of reaction leads to the related addition reaction of amine, thiol and alcohol to butadiene.View full abstractDownload PDF (904K) -
Akira MIFUNE, Atsuyuki SHIMA1977 Volume 35 Issue 2 Pages 116-130
Published: February 01, 1977
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSUnique Characteristics and various applications of Cyclodextrins are reviewed with 167 references, especially focusing on formation of their inclusion complexes and recent advances in industrial application of β-Cyclodextrin.View full abstractDownload PDF (2465K) -
Nobuo ISHIKAWA1977 Volume 35 Issue 2 Pages 131-137
Published: February 01, 1977
Released on J-STAGE: January 22, 2010
JOURNAL FREE ACCESSRecent publications on the reactions of hexafluoropropylene oxide (HFPO) were reviewed according to the following items : 1. Preparation of HFPO, 2. Properties of HFPO, 3. Rearrangements of HFPO (3.1 Reactions via pentafluoropropionyl fluoride, 3.2 Preparation of hexafluoroacetone), 4. Nucleophilic reactions, 5. Generation of difluorocarbene, 6. Reactions with perfluoroalkoxide ion.View full abstractDownload PDF (859K) -
Yoshiyuki SHINOHARA1977 Volume 35 Issue 2 Pages 138-146
Published: February 01, 1977
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSPhenol is an intermediate compound which finds its important use as the raw material for manufacturing synthetic resins, synthetic fiber, agricultural chemicals, surface active agents, etc. and today the world's annual consumption of phenol has reached approximately 3 million tons.
This compound was first isolated from coal tar by F.F. Runge in 1834 and with the development of organic chemical industry in the latter half of 19 th century, the demand for phenol increased appreciably, which in turn prompted various studies to develop processes for synthetic phenol. The first of such processes was the Sulfonation Process which is still in use by some plants operating on a small scale.
During World Wars I and II, phenol was utilized in large quantities as the raw material for producing military explosives. It was during this period that the Sulfonation Process was further improved and such other processes as Chlorination Process and Raschig Process were first commercialized.
With the growth of petrochemical industry after World War II, Cumene process was developed, which now accounts for approximately 80% of the world's phenol production.
Thereafter, phenol syntheses were attempted by such methods as toluene oxidation via benzoic acid and oxidation of cyclohexane, which, however, have been subsequently abandoned.
Either of these methods is more or less complicated and requires considerable utility consumption. Although it is theoretically possible to obtain phenol by oxidation of benzene which is in fact considered the most simplest form of phenol synthesis, but none of these methods have been found economically justifiable. It is indeed hoped that a much more simple method be developed in view of the importance of phenol as an important basic chemical.View full abstractDownload PDF (1221K) -
Fumiki MORIKAWA1977 Volume 35 Issue 2 Pages 152-156
Published: February 01, 1977
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSDownload PDF (812K)
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