| Revision as of 08:59, 18 April 2011 editCheMoBot (talk | contribs)Bots141,565 edits Updating {{chembox}} (no changed fields - added verified revid - updated 'UNII_Ref', 'ChemSpiderID_Ref', 'StdInChI_Ref', 'StdInChIKey_Ref', 'ChEMBL_Ref', 'KEGG_Ref') per Chem/Drugbox validation (← Previous edit |
Latest revision as of 00:39, 29 April 2023 edit undoTrappist the monk (talk | contribs)Administrators479,773 editsm →Coordination chemistry: cite repair;Tag: AWB |
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| verifiedrevid = 379474789 |
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| Name = Neocuproine |
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| verifiedrevid = 424658168 |
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| ImageFile = Neocuproine.gif |
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| ImageName = Neocuproine |
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| Name = Neocuproine |
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| ImageFile1 = Neocuproin.svg |
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| IUPACName = 2,9-dimethyl-1,10-phenanthroline |
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| ImageName1 = Neocuproine |
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| Section1 = {{Chembox Identifiers |
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| ImageFile = Neocuproine.jpg |
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| CASNo = 484-11-7 |
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| PIN = 2,9-Dimethyl-1,10-phenanthroline |
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| Section2 = {{Chembox Properties |
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|Section1={{Chembox Identifiers |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| Formula = C<sub>14</sub>H<sub>12</sub>N<sub>2</sub> |
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| CASNo = 484-11-7 |
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| MolarMass = 208.26 g/mol |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| Appearance = Pale Yellow solid |
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| UNII = 8E7D2SH3BV |
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| Solubility = Slightly Soluble |
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| PubChem = 65237 |
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| SolubleOther = Ethanol, Acetone, Ether, Benzene, Light Petroleum (slightly)<ref name = o'reilly>O'Reilly, E. J.; Plowman, R. A. Coordination Compounds of Substituted 1,10-Phenanthrolines and Related Dipyridyls. ''Australian Journal of Chemistry'', 13(1) '''1959''', p.145-149. doi: 10.1071/CH9600145</ref> |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| MeltingPt = 162-164 °C |
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| ChemSpiderID = 58734 |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI = 91222 |
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| EINECS = 207-601-9 |
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| SMILES = n1c3c(ccc1C)ccc2ccc(nc23)C |
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| InChI = 1/C14H12N2/c1-9-3-5-11-7-8-12-6-4-10(2)16-14(12)13(11)15-9/h3-8H,1-2H3 |
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| InChIKey = IYRGXJIJGHOCFS-UHFFFAOYAL |
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| StdInChI_Ref = {{stdinchicite|changed|chemspider}} |
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| StdInChI = 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 |
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| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}} |
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| StdInChIKey = IYRGXJIJGHOCFS-UHFFFAOYSA-N }} |
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|Section2={{Chembox Properties |
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| C=14 | H=12 | N=2 |
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| Appearance = Pale yellow solid |
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| Solubility = Slightly soluble |
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| SolubleOther = Ethanol, Acetone, Ether, Benzene, Light Petroleum (slightly)<ref name = "o'reilly">{{cite journal | author1 = O'Reilly, E. J. | author2 = Plowman, R. A. | title = Coordination Compounds of Substituted 1,10-Phenanthrolines and Related Dipyridyls | journal = Australian Journal of Chemistry | volume = 13 | issue = 1 | year = 1959 | pages = 145–149 | doi = 10.1071/CH9600145}}</ref> |
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| MeltingPtC = 162 to 164 |
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'''Neocuproine''' is a ] ] and ]. ] 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.<ref>Eggleston, M. K., P. E. Fanwick, A. J. Pallenberg, D. R. McMillin "A Twist on the Copper Center in the Crystal Structure of PF<sub>6</sub> and the Charge-Transfer Excited State? (dnpp = 2,9-Dineopentyl-1,10-phenanthroline)" Inorganic Chemistry, 1997, volume 36, p. 4007-4010.{{DOI|10.1021/ic970135e}}</ref><ref name = chandler>Chandler, Christopher J.; Deady, Leslie W.; Reiss, James A. Synthesis of some 2,9-Disubstituted-1,10-phenanthrolines. ''Journal of Heterocyclic Chemistry'' 18, '''1981''', p.599-601. {{doi|10.1002/jhet.5570180332}}</ref> |
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'''Neocuproine''' is a ] ] and ]. ] 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.<ref>{{cite journal | author1 = M. K. Eggleston | author2 = P. E. Fanwick | author3 = A. J. Pallenberg | author4 = D. R. McMillin | title = A Twist on the Copper Center in the Crystal Structure of PF<sub>6</sub> and the Charge-Transfer Excited State? (dnpp = 2,9-Dineopentyl-1,10-phenanthroline) | journal = Inorganic Chemistry | year = 1997 | volume = 36 | issue = 18 | pages = 4007–4010 | doi = 10.1021/ic970135e}}</ref><ref name = chandler>{{cite journal | author1 = Chandler, Christopher J. | author2 = Deady, Leslie W. | author3 = Reiss, James A. | title = Synthesis of some 2,9-Disubstituted-1,10-phenanthrolines | journal = Journal of Heterocyclic Chemistry | volume = 18 | year = 1981 | issue = 3 | pages = 599–601 | doi = 10.1002/jhet.5570180332}}</ref> |
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==Synthesis and structure== |
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==Synthesis and structure== |
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Neocuproine can be prepared by sequential ]s (]/condensation) of o-nitroaniline (]) with crotonaldehyde diacetate: |
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Neocuproine can be prepared by sequential ]s (]/condensation) of o-nitroaniline (]) with crotonaldehyde diacetate. An alternate synthesis involves the condensation of ], m-nitrobenzenesulphonate, and crotonaldehyde diacetate. This method gives higher yields but is less economical.<ref name = "o'reilly"/> Neocuproine crystallizes as a ] and a hemihydrate. |
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<sub>2</sub>.|260px|left]] |
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An alternate synthesis involves the condensation of ], m-nitrobenzenesulphonate, and crotonaldehyde diacetate. This method gives higher yields but is less economical.<ref name = o'reilly/> |
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==Coordination chemistry== |
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Neocuproine crystalizes as a ] and a hemihydrate as well as a hydrated hydrochloride salt. The structure of the ] features a π-stacking motif, with additional ] between the basic nitrogen centers and water.<ref>Koroglu, Ahmet; Bulut, Ahmet; Ucar, Ibrahim; Nichol, Gary; Harrington, Ross W.; Clegg, William "A second monoclinic polymorph of 2,9-dimethyl-1,10-phenanthroline dihydrate" ''Organic Papers'', E61, '''2005''', p.3723-3725. {{doi|10.1107/S1600536805033179}}</ref> |
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In the early 1930s, ] 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, <sup>+</sup> has a deep orange-red color.<ref name = "o'reilly"/> The properties of copper(I) neocuproine complexes have been widely studied, e.g. for the preparation of ] and ] complexes.<ref>McCleverty, J; Meyer, T. J. "Phenanthroline Ligands" in Comprehensive Coordination Chemistry II, Vol. 1, '''2004''', p.25-39.</ref> The copper-catalyzed release of NO<sup>+</sup> (]) from ]s is inhibited by neocuproine.<ref>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. '']'', 121(6), '''1997''', p.1047-1050. {{doi|10.1038/sj.bjp.0701218}}</ref> |
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Relative to 1,10-], neocuproine bears steric bulk flanking the nitrogen donor sites. A major consequence is that complexes of the type <sup>n+</sup> are disfavored, in contrast to the situation with phenanthroline ligands that lack substitution in the 2,9 positions.<ref name=Pallenberg>{{cite journal|author1=Pallenberg, A. J. |author2=Marschner, T. M. |author3=Barnhart, D. M. |title=Phenanthroline complexes of the d<sup>10</sup> Metals Nickel(0), Zinc(II) and Silver(I)—Comparison to Copper(I) Species|journal=Polyhedron|year=1997|volume=16|issue=16 |pages=2711–2719|doi=10.1016/S0277-5387(97)00051-X}}</ref> The ligand ] is similar to neocuproine, but has phenyl substituents at the 4,7-positions. |
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==Coordination chemistry== |
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In the early 1930s, ] 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)<sub>2</sub><sup>+</sup> has a deep orange-red color.<ref name = o'reilly/> The properties of copper(I) neocuproine complexes have been widely studied, e.g. for the preparation of ] and ] complexes.<ref>McCleverty, J; Meyer, T. J. "Phenanthroline Ligands" in Comprehensive Coordination Chemistry II, Vol. 1, '''2004''', p.25-39.</ref> The copper-catalyzed release of NO<sup>+</sup> (]) from ]s is inhibited by neocuproine.<ref>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</ref> |
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==Other metals== |
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==Other metals== |
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Platinum forms the square planar complexes .<ref>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}}</ref> |
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Platinum forms the square planar complexes .<ref>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}}</ref> |
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Neocuproine has also been discovered to have properties that cause fragmentation and disappearance of the ] in adult ] ]. Those expressing eGFP also have been observed to lose eGFP ] in the presence of neocuproine.<ref>O’Reilly-Pol, Thomas; Johnson, Stephen L. "Neocuproine Ablates Melanocytes in Adult Zebrafish" ''Zebrafish'' 5(4). Mary Ann Liebert, Inc. '''2008'''. doi: 10.1002/ejic.200300888</ref> |
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Neocuproine has also been discovered to have properties that cause fragmentation and disappearance of the ] in adult ] ]. Those expressing eGFP also have been observed to lose eGFP ] in the presence of neocuproine.<ref>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}}</ref> |
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==References== |
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==References== |