Neocuproine is a heterocyclicorganic compound and chelating agent. Phenanthroline ligands were first published in the late 19th century, and the derivatives substituted at the 2 and 9 positions are among the most studied of the modified phenanthrolines.[2][3]
Neocuproine can be prepared by sequential Skraup reactions (Doebner-Miller reaction/condensation) of o-nitroaniline (2-Nitroaniline) with crotonaldehyde diacetate. An alternate synthesis involves the condensation of o-phenylenediamine, m-nitrobenzenesulphonate, and crotonaldehyde diacetate. This method gives higher yields but is less economical.[1] Neocuproine crystallizes as a dihydrate and a hemihydrate.
structure of [NiCl2(neocuproine)]2.
Coordination chemistryedit
In the early 1930s, phenanthroline derivatives became known for their use as colorimetric indicators for many transition metals. Neocuproine proved to be highly selective for copper(I). The resulting complex, [Cu(neocuproine)2]+ has a deep orange-red color.[1] The properties of copper(I) neocuproine complexes have been widely studied, e.g. for the preparation of catenane and rotaxane complexes.[4] The copper-catalyzed release of NO+ (nitrosonium) from S-Nitrosothiols is inhibited by neocuproine.[5]
Relative to 1,10-phenanthroline, neocuproine bears steric bulk flanking the nitrogen donor sites. A major consequence is that complexes of the type [M(neocuproine)3]n+ are disfavored, in contrast to the situation with phenanthroline ligands that lack substitution in the 2,9 positions.[6] The ligand bathocuproine is similar to neocuproine, but has phenyl substituents at the 4,7-positions.
Other metalsedit
Platinum forms the square planar complexes [PtX2(2,9-dimethyl-1,10-phenanthroline)].[7]
Neocuproine has also been discovered to have properties that cause fragmentation and disappearance of the melanin in adult zebrafishmelanocytes. Those expressing eGFP also have been observed to lose eGFP fluorescence in the presence of neocuproine.[8]
Referencesedit
^ abcO'Reilly, E. J.; Plowman, R. A. (1959). "Coordination Compounds of Substituted 1,10-Phenanthrolines and Related Dipyridyls". Australian Journal of Chemistry. 13 (1): 145–149. doi:10.1071/CH9600145.
^M. K. Eggleston; P. E. Fanwick; A. J. Pallenberg; D. R. McMillin (1997). "A Twist on the Copper Center in the Crystal Structure of [Cu(dnpp)2]PF6 and the Charge-Transfer Excited State? (dnpp = 2,9-Dineopentyl-1,10-phenanthroline)". Inorganic Chemistry. 36 (18): 4007–4010. doi:10.1021/ic970135e.
^Chandler, Christopher J.; Deady, Leslie W.; Reiss, James A. (1981). "Synthesis of some 2,9-Disubstituted-1,10-phenanthrolines". Journal of Heterocyclic Chemistry. 18 (3): 599–601. doi:10.1002/jhet.5570180332.
^McCleverty, J; Meyer, T. J. "Phenanthroline Ligands" in Comprehensive Coordination Chemistry II, Vol. 1, 2004, p.25-39.
^Al-Sa’doni, H.H.; Megson, I.L.; Bisland, S.; Butler, A.R.; Flitney, F.W. Neocuproine, A Selective Cu(I) Chelator, and the relaxation of rat vascular smooth muscle by S-nitrosothiols. British Journal of Pharmacology, 121(6), 1997, p.1047-1050. doi:10.1038/sj.bjp.0701218
^Pallenberg, A. J.; Marschner, T. M.; Barnhart, D. M. (1997). "Phenanthroline complexes of the d10 Metals Nickel(0), Zinc(II) and Silver(I)—Comparison to Copper(I) Species". Polyhedron. 16 (16): 2711–2719. doi:10.1016/S0277-5387(97)00051-X.
^Fanizzi, Francesco P.; Margiotta, Nicola; Lanfranchi, Maurizio; Tiripicchio, Antonio; Pacchioni, Gianfranco; Natile, Giovanni "A Molecular Tool for Measuring the Electron-Acceptor Ability of Ligands from Crystallographic Data" European Journal of Inorganic Chemistry volume 8, 2004, p.1705-1713. doi:10.1002/ejic.200300888
^O’Reilly-Pol, Thomas; Johnson, Stephen L. "Neocuproine Ablates Melanocytes in Adult Zebrafish" Zebrafish 5(4). Mary Ann Liebert, Inc. 2008. doi:10.1089/zeb.2008.0540
Appendix: NMR Shiftsedit
The following figures contain information on the nuclear magnetic resonance spectroscopic data of neocuproine (from Chandler et al.):
1H NMR
Substituent
Chemical Shift (δ ppm)
H-3,8
7.45
H-4,7
8.03
H-5,6
7.65
1H Decoupled 13C NMR
Substituent
Chemical Shift (δ ppm)
C-2
159.2
C-10b
145.1
C-4
136.2
C-4a
126.7
April 10, 2024
neocuproine, heterocyclic, organic, compound, chelating, agent, phenanthroline, ligands, were, first, published, late, 19th, century, derivatives, substituted, positions, among, most, studied, modified, phenanthrolines, namespreferred, iupac, name, dimethyl, p. Neocuproine is a heterocyclic organic compound and chelating agent Phenanthroline ligands were first published in the late 19th century and the derivatives substituted at the 2 and 9 positions are among the most studied of the modified phenanthrolines 2 3 Neocuproine NamesPreferred IUPAC name 2 9 Dimethyl 1 10 phenanthrolineIdentifiersCAS Number 484 11 7 Y3D model JSmol Interactive imageChEBI CHEBI 91222 YChemSpider 58734 YECHA InfoCard 100 006 911EC Number 207 601 9PubChem CID 65237UNII 8E7D2SH3BV YCompTox Dashboard EPA DTXSID5060065InChI InChI 1S C14H12N2 c1 9 3 5 11 7 8 12 6 4 10 2 16 14 12 13 11 15 9 h3 8H 1 2H3 NKey IYRGXJIJGHOCFS UHFFFAOYSA N NInChI 1 C14H12N2 c1 9 3 5 11 7 8 12 6 4 10 2 16 14 12 13 11 15 9 h3 8H 1 2H3Key IYRGXJIJGHOCFS UHFFFAOYALSMILES n1c3c ccc1C ccc2ccc nc23 CPropertiesChemical formula C 14H 12N 2Molar mass 208 264 g mol 1Appearance Pale yellow solidMelting point 162 to 164 C 324 to 327 F 435 to 437 K Solubility in water Slightly solubleSolubility Ethanol Acetone Ether Benzene Light Petroleum slightly 1 Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa N verify what is Y N Infobox references Contents 1 Synthesis and structure 2 Coordination chemistry 3 Other metals 4 References 5 Appendix NMR ShiftsSynthesis and structure editNeocuproine can be prepared by sequential Skraup reactions Doebner Miller reaction condensation of o nitroaniline 2 Nitroaniline with crotonaldehyde diacetate An alternate synthesis involves the condensation of o phenylenediamine m nitrobenzenesulphonate and crotonaldehyde diacetate This method gives higher yields but is less economical 1 Neocuproine crystallizes as a dihydrate and a hemihydrate nbsp structure of NiCl2 neocuproine 2 Coordination chemistry editIn the early 1930s phenanthroline derivatives became known for their use as colorimetric indicators for many transition metals Neocuproine proved to be highly selective for copper I The resulting complex Cu neocuproine 2 has a deep orange red color 1 The properties of copper I neocuproine complexes have been widely studied e g for the preparation of catenane and rotaxane complexes 4 The copper catalyzed release of NO nitrosonium from S Nitrosothiols is inhibited by neocuproine 5 Relative to 1 10 phenanthroline neocuproine bears steric bulk flanking the nitrogen donor sites A major consequence is that complexes of the type M neocuproine 3 n are disfavored in contrast to the situation with phenanthroline ligands that lack substitution in the 2 9 positions 6 The ligand bathocuproine is similar to neocuproine but has phenyl substituents at the 4 7 positions Other metals editPlatinum forms the square planar complexes PtX2 2 9 dimethyl 1 10 phenanthroline 7 Neocuproine has also been discovered to have properties that cause fragmentation and disappearance of the melanin in adult zebrafish melanocytes Those expressing eGFP also have been observed to lose eGFP fluorescence in the presence of neocuproine 8 References edit a b c O Reilly E J Plowman R A 1959 Coordination Compounds of Substituted 1 10 Phenanthrolines and Related Dipyridyls Australian Journal of Chemistry 13 1 145 149 doi 10 1071 CH9600145 M K Eggleston P E Fanwick A J Pallenberg D R McMillin 1997 A Twist on the Copper Center in the Crystal Structure of Cu dnpp 2 PF6 and the Charge Transfer Excited State dnpp 2 9 Dineopentyl 1 10 phenanthroline Inorganic Chemistry 36 18 4007 4010 doi 10 1021 ic970135e Chandler Christopher J Deady Leslie W Reiss James A 1981 Synthesis of some 2 9 Disubstituted 1 10 phenanthrolines Journal of Heterocyclic Chemistry 18 3 599 601 doi 10 1002 jhet 5570180332 McCleverty J Meyer T J Phenanthroline Ligands in Comprehensive Coordination Chemistry II Vol 1 2004 p 25 39 Al Sa doni H H Megson I L Bisland S Butler A R Flitney F W Neocuproine A Selective Cu I Chelator and the relaxation of rat vascular smooth muscle by S nitrosothiols British Journal of Pharmacology 121 6 1997 p 1047 1050 doi 10 1038 sj bjp 0701218 Pallenberg A J Marschner T M Barnhart D M 1997 Phenanthroline complexes of the d10 Metals Nickel 0 Zinc II and Silver I Comparison to Copper I Species Polyhedron 16 16 2711 2719 doi 10 1016 S0277 5387 97 00051 X Fanizzi Francesco P Margiotta Nicola Lanfranchi Maurizio Tiripicchio Antonio Pacchioni Gianfranco Natile Giovanni A Molecular Tool for Measuring the Electron Acceptor Ability of Ligands from Crystallographic Data European Journal of Inorganic Chemistry volume 8 2004 p 1705 1713 doi 10 1002 ejic 200300888 O Reilly Pol Thomas Johnson Stephen L Neocuproine Ablates Melanocytes in Adult Zebrafish Zebrafish 5 4 Mary Ann Liebert Inc 2008 doi 10 1089 zeb 2008 0540Appendix NMR Shifts editThe following figures contain information on the nuclear magnetic resonance spectroscopic data of neocuproine from Chandler et al 1H NMR Substituent Chemical Shift d ppm H 3 8 7 45H 4 7 8 03H 5 6 7 651H Decoupled 13C NMR Substituent Chemical Shift d ppm C 2 159 2C 10b 145 1C 4 136 2C 4a 126 7 Retrieved from https en wikipedia org w index php title Neocuproine amp oldid 1152236243, wikipedia, wiki, book, books, library,
