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Volume 27, Issue 8
Displaying 1-12 of 12 articles from this issue
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Junji FURUKAWA1969 Volume 27 Issue 8 Pages 691-700
Published: August 01, 1969
Released on J-STAGE: November 13, 2009
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Tadashi SUEHIRO1969 Volume 27 Issue 8 Pages 701-714
Published: August 01, 1969
Released on J-STAGE: November 13, 2009
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Takeo SATO1969 Volume 27 Issue 8 Pages 715-730
Published: August 01, 1969
Released on J-STAGE: January 22, 2010
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Seiichiro OGAWA1969 Volume 27 Issue 8 Pages 731-746
Published: August 01, 1969
Released on J-STAGE: November 13, 2009
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The Hydrosilane Reduction IVYoichiro NAGAI, Hideyuki MATSUMOTO, Tomio YAGIHARA, Katsushi MORISHITA1969 Volume 27 Issue 8 Pages 747-753
Published: August 01, 1969
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSA hydrogen-halogen exchange reaction between a hydrosilane and a chloroalkane or a bromoalkane was found to occur under rather mild conditions in the presence of chloroplatinic acid as a catalyst. For example, carbon tetrachloride was treated with triethylsilane at 75°C for 10 hr to obtain chloroform and triethylchlorosilane in 68 and 95% yields respectively. Varieties of gem-polyhaloalkanes were similarly reduced with ease to form mainly the first step reduction products. In general, the yield of the halosilane was almost quantitative, whereas that of the reduced haloalkane was rather poor. The feature of this reaction and that of the previously reported homolytic reduction by hydrosilane are much alike.
Thus, the reactivity of halogen atoms decreases in the following order : -CCl2-Cl>-CHCl-Cl>-CH2-Cl2 secondary C-Cl>primary C-Cl, and Br>Cl.View full abstractDownload PDF (1013K) -
Masaharu NISHI, Shigeo TANIMOTO, Masaya OKANO, Ryohei ODA1969 Volume 27 Issue 8 Pages 754-758
Published: August 01, 1969
Released on J-STAGE: January 21, 2010
JOURNAL FREE ACCESSAryl magnesium bromides were treated with N, N-dimethylformamide dimethylacetal (DMFDA) in tetrahydrofuran to obtain the corresponding 1, 1-diaryltrimethylamines.
2ArMgBr+CH3_??_CH3_??_N-CH_??_OCH3_??_OCH3→CH3_??_CH3_??_N-CH_??_Ar_??_Ar
Ar = C6H5, p-CF3OC6H4, o-CH3OC6H4, p-CH3C6H4, m-CH3C6H4, o-CH3C6H4
N'-Arylarylamidines reacted with an exess amount of DMFDA to afford the corresponding N-dimethylaminomethylideneamidines, as follows :
ArC_??_NH2_??_NAr'+CH3_??_CH3_??_N-CH_??_OCH3_??_OCH3→ArC_??_N=CH-N_??_CH3_??_CH3_??_NAr'
Ar =p-CH3C6H4 Ar' C6H5, Ar C6H5 Ar' C6H5, Ar = 2-C10H7 Ar' = C6H5, Ar =p-ClC6H4 Ar' = C6H5, Ar C6H5 Ar' =p-ClC6H4
Condensation reactions of o-aminobenzamide and o-aminobenzenesulfamide with DMFDA or ethyl orthoformate yielded 4-keto-3, 4-dihydroquinazoline and 2H-1, 2, 4-benzothiadiazine 1, 1-dioxide, respectively.View full abstractDownload PDF (609K) -
Studies on the Water-Soluble Polymers. XIXSeishi MACHIDA, Keizo MATSUO1969 Volume 27 Issue 8 Pages 759-763
Published: August 01, 1969
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSTwo isomeric acrylic acid derivatives, crotonic acid and isocrotonic acid, failed to homopolymerize by the radical reaction. They, however, copolymerized with acrylamide and 2-methyl-N-vinylimidazole to some extent. They showed a slightly higher reactivity with 2-methyl-N-vinylimidazole than with acrylamide, and the reactivity of isocrotonic acid was higher than that of crotonic acid. The monomer reactivity ratios were determined, as follows :
for isocrotonic acid (1) - acrylamide (2), r1 =0.11, r2=4.72;
for crotonic acid (1) - acrylamide (2), r1=0.12, r2=5.32;
for isocrotonic acid (1) - 2-methyl-N-vinylimidazole (2), r1=0.60, r2=0.09;
for crotonic acid (1) - 2-methyl-N-vinylimidazole (2), r1 =0.49, r2=0.19.
It is confirmed that, in the radical copolymerization, the reactivity of the isomers can not be explained only by the thermodynamic stability. Other factors such as inductive, resonance, and steric effects of the substituents must also be taken into consideration. The comparative reactivities of the isomers of α, β-disubstituted olefins may be predicted based on the inductive substituent constants of theα-and β-substituents.View full abstractDownload PDF (730K) -
Studies of the Water-Soluble Polymers. XXSeishi MACHIDA, Takao ASHIDA1969 Volume 27 Issue 8 Pages 764-768
Published: August 01, 1969
Released on J-STAGE: January 22, 2010
JOURNAL FREE ACCESSA polyacrylamide of mean degree of polymerization of about 10, 000 was treated with acetaldehyde to obtain a water-soluble derivatives. The reaction was markedly affected by the pH of reaction medium, as the polymer tended to gel under acidic conditions. Water-soluble polymers were obtainable in a pH range of 2.63.3 at 60°C. Under those conditions, a higher degree of condensation was effected by lower pH values, higher temperatures and larger amounts of acetaldehyde added. When the degree of condensation was less than 70%, the polymer was watersoluble. Their viscosities became higher as the degrees of condensation increased. The chemical structures of the polymer were investigated by means of infra-red spectroscopy. It was found that the polymers served as excellent flocculating agents for caolin dispersion. Their flocculating effects were proportional to the intrinsic viscosities or the degrees of condensation. It is notable that the aggregates once subsided are hardly redispersed.View full abstractDownload PDF (740K) -
Hiroza MITOGUCHI, Yasuo KIKUCHI, Katsuaki KIMURA1969 Volume 27 Issue 8 Pages 769-774
Published: August 01, 1969
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSElectroinitiated polymerization of acenaphthylene was found to occur in acetic anhydride or acetonitrile containing lithium perchlorate, potassium perchlorate, potassium fluoroborate, or tetra-n-butylammonium bromide at -7830°C.
The average molecular weights of the polymers obtained were in the range of 2, 0003, 000, much lower that of polyacenaphthylene prepared by the ordinary polymerization.
Results of the infra-red and visible spectroscopic studies indicated the presence of an acetoxy groups, possibly introduced by the termination reaction, in the polymers formed in acetic anhydride. Otherwise, the structures of those polymers were similar to that obtained by the ordinary polymerization.
The reaction mechanism has been discussed on the basis of Breitenbach's experiments.View full abstractDownload PDF (837K) -
Nobuyuki GOTOH, Yoshio NAGAI, Sumio TOKITA, Takeo YUASA1969 Volume 27 Issue 8 Pages 775-782
Published: August 01, 1969
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESS9, 9'-Dihalogeno-3, 3-dibenzanthronyls were prepared as intermediates for the synthesis of diviolanthronyl, a possible high molecular weight dyestuff or a possible electric semiconductor. They were fine yellow crystals and dissolved in concentrated sulfuric acid to give a dark red solution.
The 9, 9'-dichloro derivative, mp 4425°C, of 3, 3'-dibenzanthronyl (6) was prepared by the dehydrogenation condensation of 9-chlorobenzanthrone in the presence of magnesium dioxide. 9-Chlorobenzanthrone was obtained by the condensation of α-naphthyl-m-chlorophenylketone in the presence of aluminum chloride or by the partial reduction of 4, 9-dichlorobenzanthrone.
Though the 9, 9'-diiodo derivatve, mp 4168°C, of (6) was synthesized in a similar manner from 9-iodobenzanthrone, the reaction was extremely slow and the yield was only 18%. 9-iodo-benzanthrone, mp 1979°C, was prepared in 88% yield by the Griess reaction of 9-aminobenzanthrone in concentrated sulfuric acid.
When (6) was treated with an excessive amount of bromine, 9, 9'-dibromo-3, 3'- dibenzanthronyl, mp 4414°C, was obtained in 64% yield. The product was identical with the authentic sample obtained by the dehydrogenation condensation of 9- bromobezanthrone. The 9, 9'-dibromo derivative was also prepared by the bromination of (6) in the presence of catalysts such as aluminum halides.View full abstractDownload PDF (1429K) -
Tadatomo ASAOKA, Choichiro SHIMASAKI, Kouzo TAKI, Mamoru FUNAYAMA, Mas ...1969 Volume 27 Issue 8 Pages 783-785
Published: August 01, 1969
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSThe Friedel-Crafts self-condensation of benzyl chloride has been chosen as a means to evaluate the catalytic activities of about 50 kinds of metal halides. The lowest temperature required for initiating the reaction served as an index for the activity.
The order of the activities was in agreement with that found in the ordinary Friedel-Crafts reactions. The results are discussed in the light of the electrosolution voltage and electro-negativity of metal halides.View full abstractDownload PDF (338K) -
Takashi AKIYAMA1969 Volume 27 Issue 8 Pages 786-791
Published: August 01, 1969
Released on J-STAGE: November 13, 2009
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