Lanthanide(III) nitrobenzenesulfonates and p-toluenesulfonate complexes of lanthanide(III), iron(III), and copper(II) as novel catalysts for the formation of calix[4]resorcinarene

Karen Deleersnyder, H. Mehdi, I. Horváth, Koen Binnemans, Tatjana N. Parac-Vogt

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

Lanthanide(III) salts of p-toluenesulfonic acid [lanthanide(III) tosylates, Ln(TOS)3] and nitrobenzenesulfonic acid [Ln(NBSA)3], and p-toluenesulfonate complexes of iron(III) and copper(II) were prepared, characterized, and examined as catalysts for the synthesis of resorcinol-derived calix[4]resorcinarenes. The reaction of resorcinol with benzaldehyde yields two isomers, the all-cis isomer (rccc) and the cis-trans-trans isomer (rctt) with the relative isomer ratios depending on the reaction conditions. However, in the reaction of resorcinol with octanal only one isomer, the all-cis isomer, is formed in high yields with less than 0.1 mol % of Yb(TOS)3. Examination of lanthanide(III) tosylates and lanthanide(III) nitrobenzenesulfonates revealed that ytterbium(III) 4-nitrobenzenesulfonate [ytterbium(III) nosylate, Yb(4-NBSA)3] and ytterbium(III) 2,4-dinitrobenzenesulfonate [Yb(2,4-NBSA)3] are the most active catalysts. The catalysts could be easily recovered and reused several times for resorcinarene formation without loss of efficiency. Surprisingly good results were also obtained with iron(III) and copper(II) p-toluenesulfonates. Besides optimizing the reaction conditions, new insights into the reaction mechanism were also obtained.

Original languageEnglish
Pages (from-to)9063-9070
Number of pages8
JournalTetrahedron
Volume63
Issue number37
DOIs
Publication statusPublished - Sep 10 2007

Fingerprint

Lanthanoid Series Elements
Ytterbium
Isomers
Copper
Iron
Catalysts
Salts
4-toluenesulfonic acid
resorcinarene
resorcinol
Acids
3-nitrobenzenesulfonic acid

Keywords

  • Catalysis
  • Lanthanides
  • Lewis acids
  • Macrocycles
  • Rare earths

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry
  • Drug Discovery

Cite this

Lanthanide(III) nitrobenzenesulfonates and p-toluenesulfonate complexes of lanthanide(III), iron(III), and copper(II) as novel catalysts for the formation of calix[4]resorcinarene. / Deleersnyder, Karen; Mehdi, H.; Horváth, I.; Binnemans, Koen; Parac-Vogt, Tatjana N.

In: Tetrahedron, Vol. 63, No. 37, 10.09.2007, p. 9063-9070.

Research output: Contribution to journalArticle

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abstract = "Lanthanide(III) salts of p-toluenesulfonic acid [lanthanide(III) tosylates, Ln(TOS)3] and nitrobenzenesulfonic acid [Ln(NBSA)3], and p-toluenesulfonate complexes of iron(III) and copper(II) were prepared, characterized, and examined as catalysts for the synthesis of resorcinol-derived calix[4]resorcinarenes. The reaction of resorcinol with benzaldehyde yields two isomers, the all-cis isomer (rccc) and the cis-trans-trans isomer (rctt) with the relative isomer ratios depending on the reaction conditions. However, in the reaction of resorcinol with octanal only one isomer, the all-cis isomer, is formed in high yields with less than 0.1 mol {\%} of Yb(TOS)3. Examination of lanthanide(III) tosylates and lanthanide(III) nitrobenzenesulfonates revealed that ytterbium(III) 4-nitrobenzenesulfonate [ytterbium(III) nosylate, Yb(4-NBSA)3] and ytterbium(III) 2,4-dinitrobenzenesulfonate [Yb(2,4-NBSA)3] are the most active catalysts. The catalysts could be easily recovered and reused several times for resorcinarene formation without loss of efficiency. Surprisingly good results were also obtained with iron(III) and copper(II) p-toluenesulfonates. Besides optimizing the reaction conditions, new insights into the reaction mechanism were also obtained.",
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T1 - Lanthanide(III) nitrobenzenesulfonates and p-toluenesulfonate complexes of lanthanide(III), iron(III), and copper(II) as novel catalysts for the formation of calix[4]resorcinarene

AU - Deleersnyder, Karen

AU - Mehdi, H.

AU - Horváth, I.

AU - Binnemans, Koen

AU - Parac-Vogt, Tatjana N.

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N2 - Lanthanide(III) salts of p-toluenesulfonic acid [lanthanide(III) tosylates, Ln(TOS)3] and nitrobenzenesulfonic acid [Ln(NBSA)3], and p-toluenesulfonate complexes of iron(III) and copper(II) were prepared, characterized, and examined as catalysts for the synthesis of resorcinol-derived calix[4]resorcinarenes. The reaction of resorcinol with benzaldehyde yields two isomers, the all-cis isomer (rccc) and the cis-trans-trans isomer (rctt) with the relative isomer ratios depending on the reaction conditions. However, in the reaction of resorcinol with octanal only one isomer, the all-cis isomer, is formed in high yields with less than 0.1 mol % of Yb(TOS)3. Examination of lanthanide(III) tosylates and lanthanide(III) nitrobenzenesulfonates revealed that ytterbium(III) 4-nitrobenzenesulfonate [ytterbium(III) nosylate, Yb(4-NBSA)3] and ytterbium(III) 2,4-dinitrobenzenesulfonate [Yb(2,4-NBSA)3] are the most active catalysts. The catalysts could be easily recovered and reused several times for resorcinarene formation without loss of efficiency. Surprisingly good results were also obtained with iron(III) and copper(II) p-toluenesulfonates. Besides optimizing the reaction conditions, new insights into the reaction mechanism were also obtained.

AB - Lanthanide(III) salts of p-toluenesulfonic acid [lanthanide(III) tosylates, Ln(TOS)3] and nitrobenzenesulfonic acid [Ln(NBSA)3], and p-toluenesulfonate complexes of iron(III) and copper(II) were prepared, characterized, and examined as catalysts for the synthesis of resorcinol-derived calix[4]resorcinarenes. The reaction of resorcinol with benzaldehyde yields two isomers, the all-cis isomer (rccc) and the cis-trans-trans isomer (rctt) with the relative isomer ratios depending on the reaction conditions. However, in the reaction of resorcinol with octanal only one isomer, the all-cis isomer, is formed in high yields with less than 0.1 mol % of Yb(TOS)3. Examination of lanthanide(III) tosylates and lanthanide(III) nitrobenzenesulfonates revealed that ytterbium(III) 4-nitrobenzenesulfonate [ytterbium(III) nosylate, Yb(4-NBSA)3] and ytterbium(III) 2,4-dinitrobenzenesulfonate [Yb(2,4-NBSA)3] are the most active catalysts. The catalysts could be easily recovered and reused several times for resorcinarene formation without loss of efficiency. Surprisingly good results were also obtained with iron(III) and copper(II) p-toluenesulfonates. Besides optimizing the reaction conditions, new insights into the reaction mechanism were also obtained.

KW - Catalysis

KW - Lanthanides

KW - Lewis acids

KW - Macrocycles

KW - Rare earths

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