Synthesis, conformation and equilibrium study of new piperazine and azamacrocyclic ligands with N-(tetrahydro-2-oxofuran-3-yl) and N-[(carboxy)(2-hydroxyethyl)methyl] pendant arms

István Lázár, R. Király, Z. Baranyai, Zsolt Baranyai, E. Brücher, Erno Brücher

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

New piperazine (1), homopiperazine (2), 1-tosyl- 1,4,7-triazacyclononane (3), 1,4,7-triazacyclononane (4), and 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (5) derivatives 1a-5a with 2-oxotetrahydrofuran-3-yl pendant arms have been synthesized from the parent cyclic polyamines 1-5 and 2-bromobutyrolactone in acetonitrile. Their conformational properties have been studied by molecular mechanics and NMR spectroscopy, and new sets of Karplus parameters for calculation of the vicinal coupling constants of the butyrolactone moieties have been determined. Compounds 1a-5a were hydrolysed to (carboxy)(2-hydroxyethyl)methyl derivatives 1b-5b by treatment with aqueous sodium hydroxide. The protonation and complexation properties of 4b (HOET-NOTA) were studied by pH potentiometry, photometry, and 1H NMR titrations, and the results were compared with the corresponding values for NOTA. It was found that, although complexation of 4b with smaller metal ions was approximately two orders of magnitude weaker, its stability constants with the lanthanides remained unchanged.

Original languageEnglish
Pages (from-to)351-360
Number of pages10
JournalEuropean Journal of Inorganic Chemistry
Issue number2
Publication statusPublished - 2002

Fingerprint

Complexation
Conformations
Ligands
Derivatives
Photometry
Lanthanoid Series Elements
Sodium Hydroxide
Molecular mechanics
Protonation
Polyamines
Titration
Nuclear magnetic resonance spectroscopy
Metal ions
Nuclear magnetic resonance
piperazine
1,4,7-triazacyclononane
1,4,7-triazacyclononane-N,N',N''-triacetic acid
acetonitrile

Keywords

  • Complexation
  • Conformation analysis
  • Lactones
  • Macrocyclic ligands
  • NMR spectroscopy

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

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title = "Synthesis, conformation and equilibrium study of new piperazine and azamacrocyclic ligands with N-(tetrahydro-2-oxofuran-3-yl) and N-[(carboxy)(2-hydroxyethyl)methyl] pendant arms",
abstract = "New piperazine (1), homopiperazine (2), 1-tosyl- 1,4,7-triazacyclononane (3), 1,4,7-triazacyclononane (4), and 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (5) derivatives 1a-5a with 2-oxotetrahydrofuran-3-yl pendant arms have been synthesized from the parent cyclic polyamines 1-5 and 2-bromobutyrolactone in acetonitrile. Their conformational properties have been studied by molecular mechanics and NMR spectroscopy, and new sets of Karplus parameters for calculation of the vicinal coupling constants of the butyrolactone moieties have been determined. Compounds 1a-5a were hydrolysed to (carboxy)(2-hydroxyethyl)methyl derivatives 1b-5b by treatment with aqueous sodium hydroxide. The protonation and complexation properties of 4b (HOET-NOTA) were studied by pH potentiometry, photometry, and 1H NMR titrations, and the results were compared with the corresponding values for NOTA. It was found that, although complexation of 4b with smaller metal ions was approximately two orders of magnitude weaker, its stability constants with the lanthanides remained unchanged.",
keywords = "Complexation, Conformation analysis, Lactones, Macrocyclic ligands, NMR spectroscopy",
author = "Istv{\'a}n L{\'a}z{\'a}r and R. Kir{\'a}ly and Z. Baranyai and Zsolt Baranyai and E. Br{\"u}cher and Erno Br{\"u}cher",
year = "2002",
language = "English",
pages = "351--360",
journal = "Chemische Berichte",
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TY - JOUR

T1 - Synthesis, conformation and equilibrium study of new piperazine and azamacrocyclic ligands with N-(tetrahydro-2-oxofuran-3-yl) and N-[(carboxy)(2-hydroxyethyl)methyl] pendant arms

AU - Lázár, István

AU - Király, R.

AU - Baranyai, Z.

AU - Baranyai, Zsolt

AU - Brücher, E.

AU - Brücher, Erno

PY - 2002

Y1 - 2002

N2 - New piperazine (1), homopiperazine (2), 1-tosyl- 1,4,7-triazacyclononane (3), 1,4,7-triazacyclononane (4), and 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (5) derivatives 1a-5a with 2-oxotetrahydrofuran-3-yl pendant arms have been synthesized from the parent cyclic polyamines 1-5 and 2-bromobutyrolactone in acetonitrile. Their conformational properties have been studied by molecular mechanics and NMR spectroscopy, and new sets of Karplus parameters for calculation of the vicinal coupling constants of the butyrolactone moieties have been determined. Compounds 1a-5a were hydrolysed to (carboxy)(2-hydroxyethyl)methyl derivatives 1b-5b by treatment with aqueous sodium hydroxide. The protonation and complexation properties of 4b (HOET-NOTA) were studied by pH potentiometry, photometry, and 1H NMR titrations, and the results were compared with the corresponding values for NOTA. It was found that, although complexation of 4b with smaller metal ions was approximately two orders of magnitude weaker, its stability constants with the lanthanides remained unchanged.

AB - New piperazine (1), homopiperazine (2), 1-tosyl- 1,4,7-triazacyclononane (3), 1,4,7-triazacyclononane (4), and 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (5) derivatives 1a-5a with 2-oxotetrahydrofuran-3-yl pendant arms have been synthesized from the parent cyclic polyamines 1-5 and 2-bromobutyrolactone in acetonitrile. Their conformational properties have been studied by molecular mechanics and NMR spectroscopy, and new sets of Karplus parameters for calculation of the vicinal coupling constants of the butyrolactone moieties have been determined. Compounds 1a-5a were hydrolysed to (carboxy)(2-hydroxyethyl)methyl derivatives 1b-5b by treatment with aqueous sodium hydroxide. The protonation and complexation properties of 4b (HOET-NOTA) were studied by pH potentiometry, photometry, and 1H NMR titrations, and the results were compared with the corresponding values for NOTA. It was found that, although complexation of 4b with smaller metal ions was approximately two orders of magnitude weaker, its stability constants with the lanthanides remained unchanged.

KW - Complexation

KW - Conformation analysis

KW - Lactones

KW - Macrocyclic ligands

KW - NMR spectroscopy

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