Vibration spectra and rotational isomerism of chain molecules. V. 2,5-Dioxahexane, 2,5-dithiahexane, and 2-oxa-5-thiahexane.
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概要
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The Raman and infrared spectra of 2,5-dioxahexane CH<SUB>3</SUB>OCH<SUB>2</SUB>CH<SUB>2</SUB>OCH<SUB>3</SUB>, 2,5-dithiahexane CH<SUB>3</SUB>SCH<SUB>2</SUB>CH<SUB>2</SUB>SCH<SUB>3</SUB> and 2-oxa-5-thiahexane CH<SUB>3</SUB>OCH<SUB>2</SUB>CH<SUB>2</SUB>SCH<SUB>3</SUB> were measured for the gaseous, liquid, glassy and crystalline states and were correlated with the normal-vibration calculations. The rotational isomerism was studied and the following conclusions were obtained. (1) The molecular form existing in the crystalline state is a non-extended form, in contrast with the cases of the unbranched ethers or sulfides containing one oxygen or sulfur atom which take the extended all-<I>trans</I> form. (2) Many forms coexist in the gaseous, liquid and glassy states. (3) The form existing in the crystalline state is the most stable in the liquid state. It was found that the repulsive force between non-bonded hydrogen atoms is one of the important factors influencing the conformational stabilities and for 2,5-dioxahexane the dipole-dipole interaction is another important factor. The stable conformations of these molecules were correlated with those of the polyether and polythioether chains. The stable isomers of 2-oxa-5-thiahexane could be explained on the basis of the knowledge of the conformational stabilities of the unbranched ethers and sulfides. The force constants of the ethers and sulfides were satisfactorily transferred to 2-oxa-5-thiahexane.
- 公益社団法人 日本化学会の論文
著者
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Ohta Masahiro
Department Of Cardiology Mie University Graduate School Of Medicine
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Matsuura Hiroatsu
Department Of Chemistry Faculty Of Science Hiroshima University
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Ogawa Yoshiki
Department of Chemistry, Faculty of Science, University of Tokyo
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Sakakibara Masaaki
Department of Chemistry, Faculty of Science, University of Tokyo
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Harada Issei
Department of Chemistry, Faculty of Science, The University of Tokyo
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Shimanouchi Takehiko
Department of Chemistry, Faculty of Science, The University of Tokyo
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