4-hydroxy-2',6'-dinitrobiphenyl | 129001-62-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-hydroxy-2',6'-dinitrobiphenyl
• 英文别名: 4-(2,6-dinitrophenyl)phenol
• CAS: 129001-62-3
• 化学式: C₁₂H₈N₂O₅
• 分子量: 260.206
• InChiKey: MESALRJLQXNJMN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  112
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4-hydroxy-2',6'-dinitrobiphenyl 在 吡啶 、 2,3,5-三甲基吡啶 、 六甲基磷酰三胺 、 sodium hydroxide 、 9-borabicyclo[3.3.1]nonane dimer 、 四溴化碳 、 双氧水 、 sodium 、 三氯化硼 、 铁粉 、 sodium hydride 、 potassium carbonate 、 氯化铵 、 三苯基膦 、 三氟乙酸 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 氯苯 为溶剂， 反应 214.5h， 生成 3,5-bis<3-(2-formyl-3,5-dimethylphenoxy)propyl>-4-hydroxy-2',6'-bis<6-(2-formyl-3,5-dimethylphenoxy)hexanamido>biphenyl
  参考文献：
  名称：

  Pendant-capped porphyrins. 1. The synthesis of a biphenyl pendant-capped iron(III) porphyrin model of catalase

  摘要：

  A phenol pendant-capped porphyrin ((PHPCP)H2) and its iron(III) complex ((PPCP)Fe(III)) have been synthesized. H-1 and C-13 NMR were used to characterize all intermediates leading to the final product. In addition, the heteronuclear C-13-H-1 shift correlation experiment was used to further characterize the tetraaldehyde precursor of the pendant-capped porphyrin. Proton and carbon chemical shifts for the free base porphyrin (PHPCP)H2 were assigned by using one-dimensional NMR experiments (including C-13 APT) and two-dimensional homonuclear COSY and ROESY experiments. In (PHPCP)H2, the phenol that provides the ligand is hung from the ceiling of a vaulted dome or tepee with protected walls supported by four legs that are anchored to the 2-position of the phenyl rings at the 5,10,15,20-meso-carbons of (TPP)H2. In the ground-state structure of (PPCP)Fe(III), the phenol is dissociated such that the resultant phenolate species is ligated to the high-spin (S = 5/2) iron(III). Ligation of phenolate and iron moieties is established by (i) comparison of H-1 NMR to the H-1 NMR of the phenolate complex of [(TPP)Fe(III)]+; (ii) comparison of the UV/vis spectrum to that for the phenolate complex of [(TPP)Fe(III)]+; (iii) disappearance of the O-H stretch in the IR accompanying complexation of (PHPCP)H2 with Fe(III); and (iv) laser desorption mass spectroscopy. At the active site of catalase, the protoporphyrin-IX iron(III) is ligated to the phenolate form of a tyrosine residue.

  DOI：

  10.1021/ja00021a042
• 作为产物：
  描述：

  2,6-二硝基氯苯 在 三溴化硼 、 铜 作用下， 以 二氯甲烷 为溶剂， 反应 17.0h， 生成 4-hydroxy-2',6'-dinitrobiphenyl
  参考文献：
  名称：

  First synthesis of a pendant-capped porphyrin. A biphenyl pendant-capped porphyrin model of catalase

  摘要：

  DOI：

  10.1021/ja00173a062

文献信息

• Copper-Mediated Vicarious Substitution of 1,3-Dinitrobenzene with lodophenols or lodomethyl Phenyl Sulfoxide/Sulfone
  作者：Olof Haglund、Abdul A. K. M. Hai、Martin Nilsson

  DOI：10.1055/s-1990-27061

  日期：——

  1,3-Dinitrobenzene reacts with 4-iodophenol or 2-iodophenol in the presence of copper(I) tert-butoxide and pyridine to give 2′,6′- dinitrobiphenyl-4-ol and 1-nitrodibenzofuran, respectively, in good yield. Similarly, iodomethyl phenyl sulfone or sulfoxide and 1,3-dinitrobenzene are selectively converted into 2,6-dinitrobenzyl phenyl sulfone and sulfoxide, respectively. We believe that the reactions proceed via Meisenheimer intermediates formed from 1,3-dinitrobenzene and the iodophenol, from which a proton and copper(I) iodide are eliminated. The result is a copper-mediated, selective vicarious nucleophilic substitution of hydrogen at C-2 of 1,3-dinitrobenzene.

  在叔丁醇铜（I）和吡啶存在下，1,3-二硝基苯与 4-碘苯酚或 2-碘苯酚反应，分别生成 2′,6′-二硝基联苯-4-醇和 1-硝基二苯并呋喃，收率很高。同样，碘甲基苯砜或亚砜和 1,3-二硝基苯也可选择性地分别转化为 2,6-二硝基苯基苯砜和亚砜。我们认为，这些反应是通过 1,3-二硝基苯和碘苯酚形成的迈森海默中间体进行的。结果是在铜的介导下，1,3-二硝基苯 C-2 处的氢发生了选择性替代亲核置换。
• HAGLUND, OLOF;HAI, ABDUL A. K. M.;NILSSON, MARTIN, SYNTHESIS,(1990) N0, C. 942-944
  作者：HAGLUND, OLOF、HAI, ABDUL A. K. M.、NILSSON, MARTIN

  DOI：——

  日期：——
• First synthesis of a pendant-capped porphyrin. A biphenyl pendant-capped porphyrin model of catalase
  作者：Chang Hee Lee、Barbara Garcia、Thomas C. Bruice

  DOI：10.1021/ja00173a062

  日期：1990.8
• Pendant-capped porphyrins. 1. The synthesis of a biphenyl pendant-capped iron(III) porphyrin model of catalase
  作者：Barbara Garcia、Chang Hee Lee、Andrei Blasko、Thomas C. Bruice

  DOI：10.1021/ja00021a042

  日期：1991.10

  A phenol pendant-capped porphyrin ((PHPCP)H2) and its iron(III) complex ((PPCP)Fe(III)) have been synthesized. H-1 and C-13 NMR were used to characterize all intermediates leading to the final product. In addition, the heteronuclear C-13-H-1 shift correlation experiment was used to further characterize the tetraaldehyde precursor of the pendant-capped porphyrin. Proton and carbon chemical shifts for the free base porphyrin (PHPCP)H2 were assigned by using one-dimensional NMR experiments (including C-13 APT) and two-dimensional homonuclear COSY and ROESY experiments. In (PHPCP)H2, the phenol that provides the ligand is hung from the ceiling of a vaulted dome or tepee with protected walls supported by four legs that are anchored to the 2-position of the phenyl rings at the 5,10,15,20-meso-carbons of (TPP)H2. In the ground-state structure of (PPCP)Fe(III), the phenol is dissociated such that the resultant phenolate species is ligated to the high-spin (S = 5/2) iron(III). Ligation of phenolate and iron moieties is established by (i) comparison of H-1 NMR to the H-1 NMR of the phenolate complex of [(TPP)Fe(III)]+; (ii) comparison of the UV/vis spectrum to that for the phenolate complex of [(TPP)Fe(III)]+; (iii) disappearance of the O-H stretch in the IR accompanying complexation of (PHPCP)H2 with Fe(III); and (iv) laser desorption mass spectroscopy. At the active site of catalase, the protoporphyrin-IX iron(III) is ligated to the phenolate form of a tyrosine residue.