@article{oai:niigata-u.repo.nii.ac.jp:00002568,
 author = {今泉, 洋 and 斎藤, 博美 and 狩野, 直樹},
 issue = {4},
 journal = {Radioisotopes, Radioisotopes},
 month = {Apr},
 note = {トリチウム標識ボリ(ビニルアルコール)と各種脂肪族ジアミンとの間で,水素同位体交換反応(T-for-H交換反応)が,50～90℃の温度範囲で観測された。その結果,反応時間の増加とともに,ジアミンの放射能の増加が認められた。このようにして得られた観測データにA"-McKayプロット法を適用することで,この反応の速度定数(k)を得た。このようにして得たkを用いて,ジアミン中のメチレンの数とその反応性との関係を定量比較できた。更に,ジアミンのアミノ基のN原子上の相対電荷がそのジアミンの反応性に及ぼす影響を明らかにするため,MOPAC法を用いた。以上の結果と以前得られた結果とから, T-for-H交換反応における脂肪族ジアミンに関して,次の五つの事柄がわかった。(1)各ジアミンの反応性は,そのジアミン中のメチレンの数が増加するにつれ,減少する。(2)ジアミン中のメチレンの数が1,3,5と増えた場合の反応性の低下率は,2,4,6と増えた場合の低下率よりも大きい。(3)幾つかの化合物の反応性に及ぼす温度の影響は,(ジカルボン酸)＜(ジアミン)＜(ジオール)＜(芳香族化合物)の順である。(4)ジアミン中のメチレンの数が奇数の場合,ジアミンのN原子の相対電荷は,メチレンの数の増加とともに減少する。偶数の場合は,ジアミンのN原子の相対電荷は,メチレンの数の増加とともに増加する。(5)本研究の手法とMOPAC法とを用いることで,ある溶媒中のジアミンの立体配置を見積もれる可能性が高い。, The hydrogen-isotope exchange reaction (T-for-H exchange reaction) between tritium-labeled poly (vinyl alcohol) and each normal chain diamine has been observed in the range of 50 to 90℃. Consequently, the activity of the diamine increased with increasing reaction time. Applying the A"-McKay plot method to the obsetved data thus obtained, the rate constants (k) for the diamines were also obtained. Using each k thus obtained, the relation between the number of methylene groups in the diamine and the reactivity of the diamine was quantitatively compared. Then, in order to clarify the effect of relative atomic charge of N atom in the ammo group on the reactivity of the diamine, the MOPAC method was used. From both the above-mentioned and the obtained previously, the following five items were found as to normal chain amines in the T-for-H exchange reaction, (l) Increasing the number of methylene groups in each diamine leads to decreasing k for the diamine. (2) The decreasing ratio of the reactivity of the diamine, where the number of methylene groups in each diamine increases from one to three (and to five), is larger than the decreasing ratio of the reactivity of the diamine, where the number of the methylene groups in the diamine increases from two to four (and to six). (3) The effect of temperature on the reactivity of several compounds is in the following order: (dicarboxylic acids) <(diamines)<(diols)<(aromatic compounds). (4) When the number of methylene groups is odd, the relative atomic charge of the N atom in the amino group decreases with increasing number of methylene groups in the diamine. When the number of methylene groups is even, the relative atomic charge of the N atom has a tendency to increase with increasing number. (5) We have a high possibility that the structure of normal chain diamine in a certain solvent may be stereo-chemically estimated by applying both the MOPAC method and the method used in this work.},
 pages = {183--190},
 title = {T-for-H交換反応における種々の直鎖状ジアミンの反応性},
 volume = {55},
 year = {2006}
}