Synthesis of proton-ionizable p-nitrophenol-containing tetraazacrown and diazadithiacrown ethers from an aromatic building block prepared via the Eionhorn reaction
- Brigham Young Univ., Provo, UT (United States). Dept. of Chemistry and Biochemistry
A series of p-nitroanisole-containing tetraazacrown, diazacryptand, and diazadithiacrown macrocycles has been prepared by treating the appropriate secondary diamine, diazacrown, or dimercaptan with 2,6-bis[(2-chloroacetamido)methyl]-4-nitroanisole (BB). Five of these p-nitroanisole-containing macrocycles were reported earlier. Four new bis(p-nitroanisole)-containing macrocycles resulting from a 2 + 2 macrocyclization of diamine or dimercaptan with BB were also isolated. Six of the p-nitroanisole-containing macrocycles were converted to the p-nitrophenol-containing macrocycles on treatment with LiI in refluxing pyridine. Thermodynamic quantities (log K, {Delta}H, and T{Delta}S) for the interactions of four new compounds with Na{sup +}, K{sup +}, Ba{sup 2+}, Ag{sup +}, and Pb{sup 2} were evaluated by calorimetric titration at 25.0 C in either 70% or absolute methanol solution. The compounds show strong interactions with Ag{sup +} and Pb{sup 2+} but very weak interactions with Na{sup +}, K{sup +}, and Ba{sup 2+}. One ligand exhibited high selectivity for Ag{sup +} over Pb{sup 2+}. X-ray crystal structures were obtained for diazadithia macrocycle and an Ag{sup +} complex.
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- FG02-86ER13463
- OSTI ID:
- 653312
- Journal Information:
- Journal of Organic Chemistry, Journal Name: Journal of Organic Chemistry Journal Issue: 14 Vol. 63; ISSN JOCEAH; ISSN 0022-3263
- Country of Publication:
- United States
- Language:
- English
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