N-(2-hydroxy-5-nitrophenyl)-N-(2-pyridylmethyl)amine

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: N-(2-hydroxy-5-nitrophenyl)-N-(2-pyridylmethyl)amine
• 英文别名: 4-Nitro-2-(pyridin-2-ylmethylamino)phenol；4-nitro-2-(pyridin-2-ylmethylamino)phenol
• 化学式: C₁₂H₁₁N₃O₃
• 分子量: 245.238
• InChiKey: RAKBWXHYXRZWDG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  91
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dichlorobis(dimethylsulfide)platinum(II) 、 N-(2-hydroxy-5-nitrophenyl)-N-(2-pyridylmethyl)amine 以 丙酮 为溶剂， 反应 48.0h， 以61%的产率得到
  参考文献：
  名称：

  配体硝基取代基在有机铂化学中与分子氧的活化或甲烷的还原消除有关的显着效果

  摘要：

  比较铂与配体 2-C 5 H 4 NCH 2 NH-C 6 H 3 -2-OH-5-R 的化学性质，当 R = H ( L ) 或 NO 2 ( L1 ) 时确定L1中硝基取代基的影响。对于无机铂 (II) 配合物，L1在 [PtCl(SMe 2 )(κ 2 - N,N'- L1 )]Cl 中作为二齿配体或在反式-[PtI 2 (SMe 2 )中作为单齿配体( κ 1 - N- L1)] 并且与甲基铂单元形成两性离子络合物 [PtMe(SMe 2 )(κ 2 - N,N'- L1 -H)]，其中包含未配位的酚盐取代基。丙酮溶液中的反应性二甲基铂络合物与分子氧反应生成羟基铂 (IV) 络合物 [Pt(OH)Me 2 (κ 3 - N,N',O- L1 -H)]，其中去质子化的L1充当fac-三齿配体。CD 2 Cl 2溶液中的二甲基铂络合物实际上以三种可能的fac-氢化二甲基铂 (IV) 异构体

  DOI：

  10.1016/j.poly.2022.115722
• 作为产物：
  描述：

  吡啶-2-甲醛 、 2-氨基-4-硝基苯酚 在 sodium tetrahydroborate 作用下， 生成 N-(2-hydroxy-5-nitrophenyl)-N-(2-pyridylmethyl)amine
  参考文献：
  名称：

  Synthesis, Structural, Magnetic, and Redox Properties of Asymmetric Diiron Complexes with a Single Terminally Bound Phenolate Ligand. Relevance to the Purple Acid Phosphatase Enzymes

  摘要：

  New asymmetrical ligands (H2L) have been synthesized to provide both a bridging and a terminal phenolate to a pair of iron ions in order to mimic the binding of a single terminal tyrosinate at the diiron center of the purple acid phosphatases. H(2)L1 is 2-[(bis(2-pyridylmethyl)amino)methyl]-6-[((2-pyridylmethyl)(2-phenol)amino of methyl]-4-methylphenol and H2L'1 and H(2)L2 are obtained by replacing the a-phenol group by the 5-nitro-2-phenol and the 6-methyl-2-phenol residues, respectively, A series of mixed valence diiron complexes [(FeFeL)-Fe-II-L-III(X)(2)](Y) have been obtained where (X)(2) is the dianion of m-phenylenedipropionate or (H2PO4)(2) and Y = BPh4 or PF6 (L = L1, Ba (X)(2) mpdp, Y = BPh4, db: (X)(2) = (OAC)(2), Y = BPh4, Ic: (X)(2) = (OBZ)(2), Y = BPh4, Id: (X)(2) = (H2PO4)(2), Y = PF6; L = L'1: 1'a (X)(2) = mpdp, Y = BPh4; L = L2: 2c: (X)(2) = (OBz)(2), Y = BPh4, 2d: (X)(2) = (H2PO4)(2), Y = PF6. Diferric complexes have been obtained also either by direct synthesis or by iodine oxidation of the mixed valence precursor (L = L1, 3a (X)(2) = mpdp, Y = BPh4, 3d: (X)(2) = (H2PO4)(2), Y = PF6; L = L2, 4d: (X)(2) = (H2PO4)(2). Y PF6. Complex la [(FeFeL)-Fe-II-L-III(mpdp)](BPh4) has been characterized by X-ray diffraction techniques, la crystallizes in the monoclinic space group P21/a with the following unit cell parameters: a 22.038 (9) Angstrom, b = 16.195 (8) Angstrom, c = 16.536 (7) Angstrom, beta = 97.26 (1)degrees, Z = 4, The significant differences in the Fe-O bond lengths indicate that the metal centers are ordered. The complexes have been studied by electronic spectral, resonance Raman, magnetic susceptibility, Mossbauer, NMR, and electrochemical techniques, Mossbauer and NMR spectroscopies concur to probe that the valences of the mixed valence compounds are trapped in solution as well as in the solid state at room temperature. The electronic spectrum of the mixed-valence compounds are dominated by a charge transfer transition in the 400-600 nm domain which moves to the 550-660 nm range upon oxidation to the diferric state. In addition they exhibit a weak and broad intervalence transition close to 1100 nm. Electrochemical studies show that the systems exist in the three redox states Fe-II/Fe-II/(FeFeIII)-Fe-II/(FeFeIII)-Fe-III. Moreover they show that the introduction of the terminal phenol group results in a thermodynamic destabilization of the diferrous state higher than the stabilization of the diferric state. An expanded stability domain of the mixed valence state is therefore observed which is probably due mostly to the asymmetry of the compounds, in addition a chemical destabilization of the reduced state of la, Ic, and 1'a is observed, Comparison of the carboxylate and phosphate derivatives leads to attribute it to the partial dissociation in solution of the carboxylate oxygen trans to the phenolate. The latter feature bears an intrinsic resemblance with the dissociation of iron which is observed when purple acid phosphatases are reduced by dithionite. These studies clearly show the importance of tyrosine binding on the redox properties of the PAP enzymes.This questions the relationship of such a redox specificity with a hydrolytic function and raises the possibility that the latter may be redox regulated or that another (redox based) function is actually involved, possibly in line with the ability of the enzymes to react with peroxides.

  DOI：

  10.1021/ja970345q

文献信息

• Synthesis, Structural, Magnetic, and Redox Properties of Asymmetric Diiron Complexes with a Single Terminally Bound Phenolate Ligand. Relevance to the Purple Acid Phosphatase Enzymes
  作者：Elisabeth Lambert、Barbara Chabut、Sylvie Chardon-Noblat、Alain Deronzier、Geneviève Chottard、Azzedine Bousseksou、Jean-Pierre Tuchagues、Jean Laugier、Michel Bardet、Jean-Marc Latour

  DOI：10.1021/ja970345q

  日期：1997.10.1

  New asymmetrical ligands (H2L) have been synthesized to provide both a bridging and a terminal phenolate to a pair of iron ions in order to mimic the binding of a single terminal tyrosinate at the diiron center of the purple acid phosphatases. H(2)L1 is 2-[(bis(2-pyridylmethyl)amino)methyl]-6-[((2-pyridylmethyl)(2-phenol)amino of methyl]-4-methylphenol and H2L'1 and H(2)L2 are obtained by replacing the a-phenol group by the 5-nitro-2-phenol and the 6-methyl-2-phenol residues, respectively, A series of mixed valence diiron complexes [(FeFeL)-Fe-II-L-III(X)(2)](Y) have been obtained where (X)(2) is the dianion of m-phenylenedipropionate or (H2PO4)(2) and Y = BPh4 or PF6 (L = L1, Ba (X)(2) mpdp, Y = BPh4, db: (X)(2) = (OAC)(2), Y = BPh4, Ic: (X)(2) = (OBZ)(2), Y = BPh4, Id: (X)(2) = (H2PO4)(2), Y = PF6; L = L'1: 1'a (X)(2) = mpdp, Y = BPh4; L = L2: 2c: (X)(2) = (OBz)(2), Y = BPh4, 2d: (X)(2) = (H2PO4)(2), Y = PF6. Diferric complexes have been obtained also either by direct synthesis or by iodine oxidation of the mixed valence precursor (L = L1, 3a (X)(2) = mpdp, Y = BPh4, 3d: (X)(2) = (H2PO4)(2), Y = PF6; L = L2, 4d: (X)(2) = (H2PO4)(2). Y PF6. Complex la [(FeFeL)-Fe-II-L-III(mpdp)](BPh4) has been characterized by X-ray diffraction techniques, la crystallizes in the monoclinic space group P21/a with the following unit cell parameters: a 22.038 (9) Angstrom, b = 16.195 (8) Angstrom, c = 16.536 (7) Angstrom, beta = 97.26 (1)degrees, Z = 4, The significant differences in the Fe-O bond lengths indicate that the metal centers are ordered. The complexes have been studied by electronic spectral, resonance Raman, magnetic susceptibility, Mossbauer, NMR, and electrochemical techniques, Mossbauer and NMR spectroscopies concur to probe that the valences of the mixed valence compounds are trapped in solution as well as in the solid state at room temperature. The electronic spectrum of the mixed-valence compounds are dominated by a charge transfer transition in the 400-600 nm domain which moves to the 550-660 nm range upon oxidation to the diferric state. In addition they exhibit a weak and broad intervalence transition close to 1100 nm. Electrochemical studies show that the systems exist in the three redox states Fe-II/Fe-II/(FeFeIII)-Fe-II/(FeFeIII)-Fe-III. Moreover they show that the introduction of the terminal phenol group results in a thermodynamic destabilization of the diferrous state higher than the stabilization of the diferric state. An expanded stability domain of the mixed valence state is therefore observed which is probably due mostly to the asymmetry of the compounds, in addition a chemical destabilization of the reduced state of la, Ic, and 1'a is observed, Comparison of the carboxylate and phosphate derivatives leads to attribute it to the partial dissociation in solution of the carboxylate oxygen trans to the phenolate. The latter feature bears an intrinsic resemblance with the dissociation of iron which is observed when purple acid phosphatases are reduced by dithionite. These studies clearly show the importance of tyrosine binding on the redox properties of the PAP enzymes.This questions the relationship of such a redox specificity with a hydrolytic function and raises the possibility that the latter may be redox regulated or that another (redox based) function is actually involved, possibly in line with the ability of the enzymes to react with peroxides.
• The remarkable effects of a ligand nitro substituent in organoplatinum chemistry related to activation of dioxygen or reductive elimination of methane
  作者：Anwar Abo-Amer、Paul D. Boyle、Richard J. Puddephatt

  DOI：10.1016/j.poly.2022.115722

  日期：2022.5

  in acetone solution reacts with dioxygen to give the hydroxoplatinum(IV) complex [Pt(OH)Me2(κ 3-N,N′,O-L1-H)], in which the deprotonated L1 acts as a fac-tridentate ligand. The dimethylplatinum complex in CD2Cl2 solution actually exists as a mixture of the three possible fac-hydridodimethylplatinum(IV) isomers [PtHMe2(κ 3-N,N′,O-L1-H)], which slowly undergo reductive elimination of methane or, in the

  比较铂与配体 2-C 5 H 4 NCH 2 NH-C 6 H 3 -2-OH-5-R 的化学性质，当 R = H ( L ) 或 NO 2 ( L1 ) 时确定L1中硝基取代基的影响。对于无机铂 (II) 配合物，L1在 [PtCl(SMe 2 )(κ 2 - N,N'- L1 )]Cl 中作为二齿配体或在反式-[PtI 2 (SMe 2 )中作为单齿配体( κ 1 - N- L1)] 并且与甲基铂单元形成两性离子络合物 [PtMe(SMe 2 )(κ 2 - N,N'- L1 -H)]，其中包含未配位的酚盐取代基。丙酮溶液中的反应性二甲基铂络合物与分子氧反应生成羟基铂 (IV) 络合物 [Pt(OH)Me 2 (κ 3 - N,N',O- L1 -H)]，其中去质子化的L1充当fac-三齿配体。CD 2 Cl 2溶液中的二甲基铂络合物实际上以三种可能的fac-氢化二甲基铂 (IV) 异构体