46 research outputs found

    Stereochemistry of heterocycles - XVIII. Configurations and preferred conformations of some 4,5-dialkyl-5-methoxymethyl-and 2,2,4-trimethyl-5-alkyl-5-methoxymethyl-1,3-dioxanes

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    A group of previously undescribed methoxymethylalkylacetoacetic esters were obtained by the reaction of monochloromethyl ether with sodium salts of alkylacetoacetic esters. The reduction of the new esters with lithium aluminum hydride gave 2-alkyl-2-methoxymethyl-butane-1,3-diols. In connection with the fact that the reduction is stereochemically regulated by the rule of asymmetric induction, the erythro isomers predominate in stereoiso-meric mixtures of the 1, 3-diols. 4,5-Dialkyl-5-methoxymethyl- and 2,2,4-trimethyl-5-alkyl-5-methoxymethyl-1,3-dioxanes (mixtures of the stereoisomers with predominance of the trans isomers) were synthesized by the condensation of 2-alkyl-2-methoxymethylbutane-1,3-diols with formaldehyde and acetone. The stereoisomers were separated by precision rectification, and their configurations and preferred conformations were proved by PMR and IR spectroscopy. The low-boiling isomers of the 1,3-dioxanes under discussion are the trans isomers, while the high-boiling isomers are the cis isomers; the preferred conformation for these isomers is a somewhat distorted chair. © 1974 Plenum Publishing Corporation

    A sequel to the passage about naming rights

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    Among many countries, "Naming Rights" practices are not rare in business now a days, however, in Japan, these phenomena are very new things, first in 2002, initially on public facilities. Besides administrative and public commercial legal studies did some examine these phenomena, this article tries to discuss as some advertising thoughts, of these origin and basic principles, as the sequel to the same author\u27s main passage.海外では先行する事象がありながらも(注1)、日本で、主として公的な施設の「名前」が、契約によって使用権として対価を伴って売買される、いわゆる「ネーミングライツ(命名権)」として認識され実践が伴ったのは、2002年以降ときわめて近年の事象である(水野、2017)。行政学、私法商法実務などでこれに対する整理も試みられているが、本稿は広告研究としてその価値の泉源を確認し、断片的ながらも、その基底的な認識に向かう議論を試みる続編である

    Steerochemistry of heterocycles. - V. Stereochemical peculiarities of 1,3-dioxanes and 1,3-dithianes

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    The stereochemical peculiarities of substituted 1,3-dioxanes and 1,3-dithianes are discussed. The high probability of the existence of flexible conformations in these series, the considerable energy preference of the 5-C-axial position in the chair conformation of 1,3-dioxanes and 1,3-dithianes, and the definite preference of the 2-C-axial position in the chair conformation of 1,3-dithianes as compared with the axial conformations of the cyclohexane type are noted. The PMR spectra of stereoisomeric 2,5-dimethyl-5-isopropyl-1,3-dioxanes, 2-methy-l5-isopropyl-1,3-dithianes, and 2,2,5-trimethyl-1,3-dithiane are described, and their configurations and preferred conformations are proved. The results of a study of the epimerization of stereoisomers of substituted 1,3-dioxanes and 1,3-dithianes are examined, and the conformational energies of individual substituents in the 5-position of these cyclic systems are calculated on the basis of this examination. © 1973 Consultants Bureau, a division of Plenum Publishing Corporation

    Stereochemistry of heterocycles - XVIII. Configurations and preferred conformations of some 4,5-dialkyl-5-methoxymethyl-and 2,2,4-trimethyl-5-alkyl-5-methoxymethyl-1,3-dioxanes

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    A group of previously undescribed methoxymethylalkylacetoacetic esters were obtained by the reaction of monochloromethyl ether with sodium salts of alkylacetoacetic esters. The reduction of the new esters with lithium aluminum hydride gave 2-alkyl-2-methoxymethyl-butane-1,3-diols. In connection with the fact that the reduction is stereochemically regulated by the rule of asymmetric induction, the erythro isomers predominate in stereoiso-meric mixtures of the 1, 3-diols. 4,5-Dialkyl-5-methoxymethyl- and 2,2,4-trimethyl-5-alkyl-5-methoxymethyl-1,3-dioxanes (mixtures of the stereoisomers with predominance of the trans isomers) were synthesized by the condensation of 2-alkyl-2-methoxymethylbutane-1,3-diols with formaldehyde and acetone. The stereoisomers were separated by precision rectification, and their configurations and preferred conformations were proved by PMR and IR spectroscopy. The low-boiling isomers of the 1,3-dioxanes under discussion are the trans isomers, while the high-boiling isomers are the cis isomers; the preferred conformation for these isomers is a somewhat distorted chair. © 1974 Plenum Publishing Corporation

    Steerochemistry of heterocycles. - V. Stereochemical peculiarities of 1,3-dioxanes and 1,3-dithianes

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    The stereochemical peculiarities of substituted 1,3-dioxanes and 1,3-dithianes are discussed. The high probability of the existence of flexible conformations in these series, the considerable energy preference of the 5-C-axial position in the chair conformation of 1,3-dioxanes and 1,3-dithianes, and the definite preference of the 2-C-axial position in the chair conformation of 1,3-dithianes as compared with the axial conformations of the cyclohexane type are noted. The PMR spectra of stereoisomeric 2,5-dimethyl-5-isopropyl-1,3-dioxanes, 2-methy-l5-isopropyl-1,3-dithianes, and 2,2,5-trimethyl-1,3-dithiane are described, and their configurations and preferred conformations are proved. The results of a study of the epimerization of stereoisomers of substituted 1,3-dioxanes and 1,3-dithianes are examined, and the conformational energies of individual substituents in the 5-position of these cyclic systems are calculated on the basis of this examination. © 1973 Consultants Bureau, a division of Plenum Publishing Corporation

    Steerochemistry of heterocycles. - V. Stereochemical peculiarities of 1,3-dioxanes and 1,3-dithianes

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    The stereochemical peculiarities of substituted 1,3-dioxanes and 1,3-dithianes are discussed. The high probability of the existence of flexible conformations in these series, the considerable energy preference of the 5-C-axial position in the chair conformation of 1,3-dioxanes and 1,3-dithianes, and the definite preference of the 2-C-axial position in the chair conformation of 1,3-dithianes as compared with the axial conformations of the cyclohexane type are noted. The PMR spectra of stereoisomeric 2,5-dimethyl-5-isopropyl-1,3-dioxanes, 2-methy-l5-isopropyl-1,3-dithianes, and 2,2,5-trimethyl-1,3-dithiane are described, and their configurations and preferred conformations are proved. The results of a study of the epimerization of stereoisomers of substituted 1,3-dioxanes and 1,3-dithianes are examined, and the conformational energies of individual substituents in the 5-position of these cyclic systems are calculated on the basis of this examination. © 1973 Consultants Bureau, a division of Plenum Publishing Corporation

    Steerochemistry of heterocycles. - V. Stereochemical peculiarities of 1,3-dioxanes and 1,3-dithianes

    No full text
    The stereochemical peculiarities of substituted 1,3-dioxanes and 1,3-dithianes are discussed. The high probability of the existence of flexible conformations in these series, the considerable energy preference of the 5-C-axial position in the chair conformation of 1,3-dioxanes and 1,3-dithianes, and the definite preference of the 2-C-axial position in the chair conformation of 1,3-dithianes as compared with the axial conformations of the cyclohexane type are noted. The PMR spectra of stereoisomeric 2,5-dimethyl-5-isopropyl-1,3-dioxanes, 2-methy-l5-isopropyl-1,3-dithianes, and 2,2,5-trimethyl-1,3-dithiane are described, and their configurations and preferred conformations are proved. The results of a study of the epimerization of stereoisomers of substituted 1,3-dioxanes and 1,3-dithianes are examined, and the conformational energies of individual substituents in the 5-position of these cyclic systems are calculated on the basis of this examination. © 1973 Consultants Bureau, a division of Plenum Publishing Corporation
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