Group Interactions in Polyelectrolytes. V. The Kinetics of the Amination of Chloromethylated Polystyrene with 2-Aminobutanol
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概要
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The amination of chloromethylated polystyrene with 2-aminobutanol in dioxane was studied. The apparent rate constatns, <I>k</I><SUB>app</SUB>, as computed by the simple second-order equation, were found to increase linearly with the degree of amination; this was in contrast with the amination with <I>n</I>-butylamine, in which the <I>k</I><SUB>app</SUB> decreased as the amination proceeded. By assuming that the reactivity of the chloromethyl group is enhanced when it is situated next to the already-aminated group as a result of the "hydrophilic effect" of the hydroxyl group, rate equations which give the elementary rate constants were derived. In the presence of a large excess of amine, the over-all kinetics can be expressed by:<BR>d<I>x</I>⁄d<I>t</I>=[<I>ab</I>⁄(3<I>k</I><SUB>1</SUB>−<I>k</I><SUB>2</SUB>)][3<I>k</I><SUB>1</SUB>(<I>k</I><SUB>1</SUB>−<I>k</I><SUB>2</SUB>)e<SUP>−3<I>k</I><SUB>1</SUB><I>at</I></SUP>+2<I>k</I><SUB>1</SUB><I>k</I><SUB>2</SUB>e<SUP>−<I>k</I><SUB>2</SUB><I>at</I></SUP>]<BR>where <I>x</I> is the concentration of chloride ions at time <I>t</I>; where <I>a</I> is the initial concentration of amine, and <I>b</I>, that of the chloromethyl group, and where <I>k</I><SUB>1</SUB> and <I>k</I><SUB>2</SUB> are the rate constants of the elementary reactions which are independent of the neighboring group and under the influence of it respectively. The values of <I>k</I><SUB>app</SUB> calculated on the basis of <I>k</I><SUB>1</SUB> and <I>k</I><SUB>2</SUB> were also found to agree with the observed values.
- 公益社団法人 日本化学会の論文
著者
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Yanagita Masaya
The Institute of Physical and Chemical Research
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Kawabe Hiroshi
The Institute of Physical and Chemical Research
関連論文
- Group Interactions in Polyelectrolytes. VII. Amination Kinetics of Chloromethylated Polystyrene with Butylamine Isomers
- Group Interactions in Polyelectrolytes. V. The Kinetics of the Amination of Chloromethylated Polystyrene with 2-Aminobutanol
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