Synthesis of New Aza Macrocyclic Diamides 2,2′‐Diaminodiphenyl Sulfide Using Crab‐Like Method

Abstract

Six new aza crown ethers (4–9) were synthesized based on the conventional route crab‐like method with the reaction of corresponding bis‐α‐chloroacetamidediphenylsulfide (BCADPS) (3) and aliphathic diamines (a–e) in refluxing acetonitrile in good yields. BCADPS (3) was synthesized with the reaction of 2,2′‐diaminodiphenyl sulfide (2) and chloroacetyl chloride. Interestingly, only the macrocyclization of BCADPS (3) with diamine (e) was led to the cryptand (9) in which methylene hydrogens were found as diastereotopic nucleis which is attributed to the rigidity of the cryptand (9). The formation of this cryptand (9) may be related the template effect of potassium ion. The structures of all compounds were confirmed using IR, 1H‐NMR, 13C‐NMR, mass spectroscopies, and elemental analysis.