Six-membered heterocycles - I. The stereoisomerism of 2-alkyl-5-hexyl-1,3-dioxanes

2-Methyl-5-hexyl- and 2-isopropyl-5-hexyl-1, 3-dioxanes have been synthesized for the first time by the condensation of 2-hexyl-1, 3-propane-diol with acetaldehyde and isobutyraldehyde, and they have been separated into their stereoisomers by fractionation in efficient columns. It has been shown by a study of their PMR spectra that the low-boiling isomers have the cis- and the high-boiling isomers the trans-configuration. A study of the PMR spectra has enabled us to show not only the configuration but also the predominant conformations of the isomers; the cis-isomer exists predominantly in the unsymmetrical boat conformation with a diequatorial location of the substituents and the trans-isomer in the chair conformation, also with a diequatorial arrangement of the substituents. © 1971 Consultants Bureau

Alkoxy compounds - XXIII. Synthesis, properties, PMR spectra, and stereochemistry of 2-alkyl-2-alkoxymethyl-1, 3-propanediols and 2, 2, 5-trialkyl-5-alkoxymethyl-1,3-dioxanes

The reduction of alkoxymethylalkylmalonic esters with lithium aluminum hydride has given previously unknown 2-alkyl-2-alkoxymethyl-1, 3-propanediols, and by the condensation of these with ketones six previously unreported 2, 2, 5-trialkyl-5-alkoxymethyl-1, 3-dioxanes have been synthesized. The PMR spectra of these compounds have been studied and the unsymmetrical boat conformation has been shown for the 2, 2, 5-trialkyl-5-alkoxymethyl-1, 3-dioxanes. The causes of the stereochemical features of the compounds mentioned are discussed. © 1971 Consultants Bureau

Stereochemistry of heterocycles - VI. Study of the conformations of 2,5-dialkyl-1,3-dioxanes by means of'dipole moments

The conformations of stereoisomeric 2,5-dialkyl-1,3-dioxanes were studied by means of dipole moments (DM), and it was shown that the low-boiling isomers have a chair conformation or a somewhat distorted symmetrical boat conformation, while the high-boiling isomers have a chair conformation with diequatorial orientation of the substituents. The DM measurements lead to values for the ketals which are closest to those calculated for the chair conformation. © 1973 Consultants Bureau, a division of Plenum Publishing Corporation

Stereochemistry of heterocycles - XVII. Configuration and conformation of some stereoisomeric 4,5-substituted 2,2-dimethyl-1,3-dioxanes

The configurations and preferred conformations in series of 4,5-dialkyl and 4,5,5-trialkylsubstituted 2,2-dimethyl-1,3-dioxanes were studied. It was proved by PMR spectroscopy that the low-boiling isomers have the cis configuration, while the high-boiling isomers have the trans configuration; moreover, all of the isomers are found in the preferred chair conformation. This conformation experiences a certain amount of distortion, the degree of which depends on the number and character of the substituents in the 5 position. © 1974 Plenum Publishing Corporation

Alkoxy compounds - XXII. Synthesis and PMR spectra of some 2-substituted 5-alkyl-5-α-alkoxyethyl-1,3-dioxanes

Six 2, 2, 5-trialkyl-5-α-alkoxyethyl-1, 3-dioxanes have been synthesized for the first time by the condensation of 2-alkyl-2-α-alkoxyethyl-1, 3-propane diols with ketones, and it has been shown by a study of their PMR spectra that they exist in the unsymmetrical boat conformation. The PMR spectra of a number of previously-synthesized 2-alkyl(aryl)-5-alkyl-5-α-alkoxyethyl-1, 3-dioxanes have been considered and it has been shown that from an analysis of the spectra it is possible to estimate the contents of geometrical isomers in a mixture. The stereochemistry of these compounds has been discussed. © 1971 Consultants Bureau

表紙

Six 2, 2, 5-trialkyl-5-α-alkoxyethyl-1, 3-dioxanes have been synthesized for the first time by the condensation of 2-alkyl-2-α-alkoxyethyl-1, 3-propane diols with ketones, and it has been shown by a study of their PMR spectra that they exist in the unsymmetrical boat conformation. The PMR spectra of a number of previously-synthesized 2-alkyl(aryl)-5-alkyl-5-α-alkoxyethyl-1, 3-dioxanes have been considered and it has been shown that from an analysis of the spectra it is possible to estimate the contents of geometrical isomers in a mixture. The stereochemistry of these compounds has been discussed. © 1971 Consultants Bureau

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

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

Alkoxy compounds - XXI. Synthesis, configuration, and conformation of some 5-alkoxymethyl-2,5-dialkyl-1,3-dioxanes

Twenty-six previously unreported 5-alkoxymethyl-2,5-dialkyl-1,3-dioxanes have been synthesized by the condensation of 2-alkoxymethyl-2-alkylpropane-1,3-diols with aldehydes. It has been shown by an analysis of the PMR spectra of these dioxanes that the 1,3-dioxanes considered are mixtures of two stereoisomers. In some cases these mixtures have been resolved into the individual isomers by vacuum fractionation in efficient columns. The configurations and conformations of the stereoisomeric 5-alkoxymethyl-2,5-dialkyl-1,3-dioxanes have been established by the NMR method; it has been shown that the lower-boiling isomers have the trans configuration and predominantly the chair conformation and the higherboiling isomers the cis configuration and predominantly an unsymmetrical boat conformation. © 1970 The Faraday Press, Inc

A sequel to the passage about naming rights

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

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