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Volume 19, Issue 6
Displaying 1-11 of 11 articles from this issue
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Tateki HAYASHI, Shoei KOMATSU1961 Volume 19 Issue 6 Pages 429-437
Published: June 01, 1961
Released on J-STAGE: October 20, 2010
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Yoshiro OGATA1961 Volume 19 Issue 6 Pages 438-448
Published: June 01, 1961
Released on J-STAGE: October 20, 2010
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Yasuo TAKAMI1961 Volume 19 Issue 6 Pages 449-452
Published: June 01, 1961
Released on J-STAGE: October 20, 2010
JOURNAL FREE ACCESSSynthesis of hexaalkyldisiloxane in good yield was made by treating a product of reaction between silicon tetrachloride and 2-2.5 moles of alcohol, without refining, with RMgX in excess and hydrolysis of the product. This method was more simple than the Sommer's method of using ethyl orthosilicate as a starting material and higher yield was obtainable. It is known that trimethylethoxysilane reacts easily with CH3MgBr or CH3MgCl and yields tetramethylsilane, but the reaction of CH3MgI and trimethylethoxysilane was found to proceeded with extreme difficulty in the writer's experiment.
Also, the synthesis of triethylchlorosilane was made by passing in hydrogen chloride gas into a sulfuric acid solution of hexaethyldisiloxane. This method however, was not applicable in the synthesis of trimethylchlorosilane.View full abstractDownload PDF (759K) -
Synthesis of Vinyl acetalsSaburo HATTORI1961 Volume 19 Issue 6 Pages 453-460
Published: June 01, 1961
Released on J-STAGE: October 20, 2010
JOURNAL FREE ACCESSA low molecular polymerization of alkyl vinyl ether has been investigated and the effect of catalyst and reaction condition for obtaining of higher yield of a dimer (namely, 1, 1-dialkoxy-3-butene) have been investigated. In this reaction, mercuric oxide-boron trifluoride or mercuric acetate-boron trifluoride catalyst (molar ratio of Hg/BF3>2), and mercuric fluoride catalyst showed superior catalyst activity and its amount was about 0.1-0.3 mole % of Hg against vinyl ether. The solvent used in the reaction had a marked effect on the yield of the dimer and using of acetone showed good result. Also, an addition of a small amount of alcohol showed a tendency of stabilizing the reaction and increasing the yield of the dimer. The product was composed of a mixture of dimer, trimer, tetramer, and high boiling fraction with general OR formula CH2:CH (CH2-CH)nCH2CH(OR)2, where n=0, 1 and 2. The structure was confirmed by chemical and physical means, and discussions were made on the mechanism of reaction.View full abstractDownload PDF (1426K) -
Oxidation of Vinyl acetalsSaburo HATTORI, Katsuhiko MATSUMOTO1961 Volume 19 Issue 6 Pages 461-463
Published: June 01, 1961
Released on J-STAGE: October 20, 2010
JOURNAL FREE ACCESSAn oxidation of vinyl acetal (namely, 1, 1-dialkoxy-3-butene) has been investigated under the condition of accompanying no hydrolysis of acetal group.(1). In case of oxidation by ozone, it gave corresponding yield of ozonide and a catalytic reductive cleavage of this gave formaldehyde and malondialdehyde monoacetal. The latter was converted easily into 1, 1, 3, 3-tetraalkoxypropane by acetalization or its condensation with guanidine gave 2-aminopyrimidine.(2). Epoxylation can be carried out by the oxidation with perbenzoic acid or by dehydrochlorination of HOCl additive of vinyl acetal with alkali to obtain corresponding 3, 4-epoxybutyraldehyde acetal.(3). Alkaline KMnO4 oxidation gave α-glycol (namely, 3, 4-dihydroxybutyraldehyde acetal).View full abstractDownload PDF (505K) -
Yoichiro NAGAI1961 Volume 19 Issue 6 Pages 464-469
Published: June 01, 1961
Released on J-STAGE: October 20, 2010
JOURNAL FREE ACCESSThe pairs of geometrical isomers of 4, 4′-dichloro-(1), 4, 4′-dibromo-(2), 4, 4′- diiodo-(3), 4, 4′-dimethyl-(4), and 4, 4′-dimethoxy-(5)-α, α′-dimethylstilbene were prepared from the hydrazones of the corresponding 4-substituted acetophenones by Vargha and Kovács's method. These compounds were converted into they corresponding geometrical isomers by the action of iodine in boiling nitrobenzene. The geometrical configurations of compounds (1) to (4) were determined by the dipole moment or the X-ray diffraction measurement, and that of compound (5) was inferred from the ultraviolet measurement. The spatial configurations thus assigned are in agreement with those deduced from the general rule for the geometrical isomerism of stilbenes that the trans- form has a higher melting point and is less soluble than the cis-form.View full abstractDownload PDF (1269K) -
Yoichiro NAGAI1961 Volume 19 Issue 6 Pages 470-473
Published: June 01, 1961
Released on J-STAGE: October 20, 2010
JOURNAL FREE ACCESSThe geometrical isomers of 3, 3′-dimethoxy (2)-, 3, 3′-dimethyl (3)-, 3, 3′-dibromo (4)-, and 3, 3′-dinitro (5)-α, α′-dimethylstilbene were prepared from the corresponding 3-substituted acetophenones by Vargha and Kovacs's method. While the hydrazones-of 3-bromo or 3-nitroacetophenone yielded both cis- and trans-(4) or (5), respectively, as was expected, the hydrazones of 3-methoxyacetophenone gave only trans-(2) or (3), respectively. The oily products considered to be another isomers of (2) or (3) were also obtained from the reaction mixtures but attempt to isolate these compounds in pure form was abandoned owing to difficulty of purification.View full abstractDownload PDF (769K) -
Yoichiro NAGAI1961 Volume 19 Issue 6 Pages 473-476
Published: June 01, 1961
Released on J-STAGE: October 20, 2010
JOURNAL FREE ACCESSThe trans-isomers of 4-bromo (2)-, 4-chloro-4′-nitro (3)-, 4-methyl-4′-nitro-(4)-, and 4-methoxy-4′-nitro (5)-dimethylstilbene were prepared from 4-substituted thioacetophenones and 1-(4-substituted phenyl)-diazoethanes by SchOnberg's method. Attempt of separation of cis-form of compounds (2) to (5) was unsuccessful. The spatial configurations of resulting olefins (2) to (5) were deduced from their reaction rates with perbenzoic acid in benzene solution. The ultraviolet absorption spectra of these compounds were investigated. trans-4-Amino-4′-nitro-α, α′-dimethyl-stilbene was obtained by partial reduction of trans-4, 4′-dinitro-α, α′-dimethylstilbene by sodium sulfide and hydrogen sulfide.View full abstractDownload PDF (700K) -
Preparation of α-aminoisobutyric acid from 2-nitropropaneChikai KIMURA1961 Volume 19 Issue 6 Pages 477-480
Published: June 01, 1961
Released on J-STAGE: October 20, 2010
JOURNAL FREE ACCESSAs one of the method of utilization of nitroparaffin, the nitro alcohol obtained by condensation with aldehyde was reduced to give corresponding amino alcohol and oxidation of this to amino acid has been attempted. 2-Amino-2-methyl-l-propanol, prepared from 2-nitropropane and formaldehyde, was used as a starting material. In the oxidation of hydroxyl group, the amino group was protected from oxidation by the benzoylation with benzoyl chloride, and the oxidation was carried out by using three kinds of oxidizing agents. It was found that potassium permanganate was the most superior oxidizing agent and the oxidation was effective to give above 90% yield of product. For debenzoylation reaction, it was treated with a dilute hydrochloric acid for deriving it into objective amino acid hydrochloride, it was dehydrochlorinated by use of amine to give α-aminoisobutyric acid. Using of aniline as the amine was suitable. Each of the above reaction was found to be proceeded smoothly. The structures of intermediate products were examined by infrared absorption spectra and the mechanisms of reactions were clarified.View full abstractDownload PDF (760K) -
Koichi MURAI, Giichi AKAZOME1961 Volume 19 Issue 6 Pages 481-486
Published: June 01, 1961
Released on J-STAGE: October 20, 2010
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Mitunobu TUMURA1961 Volume 19 Issue 6 Pages 487-490
Published: June 01, 1961
Released on J-STAGE: October 20, 2010
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