界面活性クラウンエーテル (第9報) : 長鎖アルカンアミド側鎖を有する光学活性ジオキソクラウンエーテルの合成と性質

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Two series of new crown compounds [4 : CpAsp (n), CpGlu (n), p=10-16, n=5, 6] were prepared by the cyclization of oligoethylene glycol ditosylates with the dicaesium salt of N-acyl-aspartic or -glutamic acids (Scheme-1). The yields of CpGlu (n) were generally better than those of CpAsp (n) (Table-1). The yield and specific rotation ([α]25D of the cyclization products depended on reaction temperature (2080 °C), type of alkali metal cation (M : Li, Na, K, and Cs), and leaving group (X : TsO, Cl, and Br) in the ω, ω′-disubstituted oligoethylene glycols. The results for the synthesis of C10Glu (5) are as follow : 1) under M =Cs and X=TsO, the reaction at 40 °C gave a good yield (41%) and that at 20 °C, the largest [α]25D, 2) at M=Cs and 60 °C, the dibromide gave the best yield (74%) and the dichloride, a larger [α]25D. All the products except C10, 12 Asp (6) were water-insoluble. The cloud point, cmc (critical micelle concentration), and surface tension at cmc (cmc) were determined for the aqueous solution of C12 Asp (6). These values were lower than those of the corresponding open chain compound, C12Asp (6) OH, indicating a decrease in hydrophilicity caused by cyclization of oxyethylene chains. C16Asp (5, 6) was highly efficient as a phase transfer catalyst in the halogen-exchange reaction.