Tricalixarenes and pentacalixarenes: Synthesis and complexation studies

• Published in: Journal of organic chemistry Vol. 67; no. 13; pp. 4423 - 4429
• Main Authors: Wang, JS, Gutsche, CD
• Format: Journal Article
• Language: English
• Published: WASHINGTON Amer Chemical Soc 28.06.2002; American Chemical Society
• Subjects: Chemistry; Chemistry, Organic; Exact sciences and technology; Noncondensed benzenic compounds; Organic chemistry; Physical Sciences; Preparations and properties; Science & Technology; FULLERENES; CALIXARENES; Complexation; Amine; Acetylenic compound; Aryne; Fullerenes; Trimerization; Calixarene; Aldehyde; Inclusion compound; Chemical synthesis; Ketone
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo0110808

Tricalix[4]arene 4, tricalix[5]arene 14, and pentacalix[4]arene 10 have been synthesized from O-alkylcalixarene mono- and dialdehydes by a two-step conversion to the corresponding monoethynyl ketones or diethynyl ketones followed by aryne trimerization in refluxing DMF containing a dialkylamine. The tricalixarenes 4 and 14 were converted, in turn, to calixarenes 6 and 16, which carry OH groups on the lower rim and methylenes as the bridging moieties to the benzene ring. Complexation studies with the tricalix[5]arene 16 show that it forms (a) a 1:3 complex with N,N-dimethylethylenediamine in which each calixarene unit contains a molecule of the amine, (b) a 1:1 complex with tris(aminomethyl)amine in which each calixarene unit contains one of the three arms of the guest, and (c) a 1:1 complex with C-60 in which the guest presumably resides in the cavity provided by the three calixarene units acting cooperatively.