Intercalation of Aniline and Alkylanilines into .ALPHA.-Tin(IV) Bis(hydrogenphosphate).

概要

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The intercalation reaction of aniline and alkylanilines into α-tin (IV) bis (hydrogenphosphate) (α-SnP) was conducted by mixing α-SnP and benzene solutions of the amines at 25°C for 4 days, where the amine/α-SnP molar ratio (r) was varied. Aniline was intercalated into α-SnP at r of 17.1 or higher, and its interlayer distance spreaded. In the case of toluidine and ethylaniline at r of 34.1, nitrogen/phosphorus (N/P) molar ratio and interlayer distaces of the products varied for a kind of isomers of guest molecule. That is to say, m-and p-isomers of toluidine and ethylaniline were intercalated and interlayer distance of α-SnP spreaded, whereas the corresponding o-isomers were not. The numbers of p-isomers intercalated were larger than those of m-isomers. It is considered that the steric hindrance of alkyl groups for bonding of amino groups with P-OH of α-SnP, and the differences of basicity of each isomer gave dependence of intercalation behavior of toluidine and ethylaniline into α-SnP on their isomers. In the case of intercalation of p-alkylanilines at r of 34.1, the N/P molar ratio of products decreased with increasing the number of carbon atoms in their alkyl chains. These amine molecules form a bilayer in the interlayer space of α-SnP, and their alkyl chains are inclined to the α-SnP layer by ca. 81°.
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