2-氯-4-硝基苯酚 | 30388-46-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2-氯-4-硝基苯酚
• 英文名称: 2-chloro-4-nitrophenolate
• 英文别名: Phenol, 2-chloro-4-nitro-, ion(1-)
• CAS: 30388-46-6
• 化学式: C₆H₃ClNO₃
• 分子量: 172.548
• InChiKey: BOFRXDMCQRTGII-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  68.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-氯-4-硝基苯酚 在 双氧水 、 三乙胺 、 sodium hydroxide 作用下， 以 乙醚 、 水 为溶剂， 生成 2-氯-4-硝基苯酚
  参考文献：
  名称：

  Pitfalls in Assessing the α-Effect: Reactions of Substituted Phenyl Methanesulfonates with HOO⁻, OH⁻, and Substituted Phenoxides in H₂O

  摘要：

  Toward resolving the current controversy regarding the validity of the a-effect, we have examined the reactions of Y-substituted phenyl methanesulfonates 1a-11 with HOO-, OH,- and Z-substituted phenoxides in the gas phase versus solution (H2O). Criteria examined in this work are the following: (1) Bronsted-type and Hammett plots for reactions with HOO- and OH-, (2) comparison of beta(lg) values reported previously for the reactions of Y-substituted phenyl benzenesulfonates 2a-2k with HOO- (beta(lg) = -0.73) and OH- (beta(lg) = -0.55), and for those of 1a-11 with HOO- (beta(lg) = -0.69) and OH- (beta(lg) = -1.35), and (3) Bronsted-type plot showing extreme deviation of OH- for reactions of 2,4-dintrophenyl methanesulfonate la with aryloxides, HOO-, and OH-, signifying extreme solvation vs different mechanisms. The results reveal significant pitfalls in assessing the validity of current interpretations of the alpha-effect. The extreme negative deviation by OH- must be due, in part, to the difference in their reaction mechanisms. Thus, the apparent dependence of the alpha-effect on leaving-group basicity found in this study has no significant meaning due to the difference in operating mechanisms. The current results argue in favor of a further criterion, i.e., a consistency in mechanism for the alpha-nucleophiles and normal nucleophiles.

  DOI：

  10.1021/jo101978x

文献信息

• Ketene-Forming Elimination Reactions from Aryl Thienylacetates Promoted by R₂NH/R₂NH₂⁺ in 70 mol % MeCN(aq). Effect of the β-Aryl Group
  作者：Bong Rae Cho、Sang Yong Pyun

  DOI：10.1021/jo0612978

  日期：2007.2.1

  Ketene-forming eliminations from ArCH2CO2C6H3-2-X-4-NO2 (Ar = thienyl, 1) promoted by R2NH/R2NH2+ in 70 mol % MeCN(aq) have been studied kinetically. When X = CF3 and NO2, the reactions exhibit second-order kinetics as well as β = 0.30−0.64 and |βlg| = 0.31−0.52 that decrease with a better leaving group. Hence, an E2 mechanism is evident. As the leaving group is made poorer (X = H, OCH3, and Cl), E2

  在70摩尔％MeCN（aq）中，由R 2 NH / R 2 NH 2 +促进的ArCH 2 CO 2 C 6 H 3 -2-X-4-NO 2（Ar =噻吩基，1）促进了形成烯酮的消除。进行动力学研究。当X = CF 3和NO 2时，反应表现出二级动力学，以及β= 0.30-0.64和| βlg |。= 0.31-0.52，随着离开组的改善而降低。因此，E2机制是显而易见的。由于离去基团变得更贫穷（X = H，OCH 3，以及Cl），E2跃迁状态更趋向于质子转移，正如Brönstedβ增加到0.5-0.64所揭示的那样，并且E1cb机理相互竞争。随着反应物结构的变化，k 1和k -1 / k 2值的变化为竞争的E1cb机制提供了额外的支持。通过与4-YC 6 H 4 CH 2 CO 2 C 6 H 3 -2-X-4-NO 2的现有数据进行比较，评估了β-芳基对乙烯酮形成消除的影响。
• Ketene-Forming Eliminations from Aryl Phenylacetates Promoted by R₂NH/R₂NH₂⁺ in Aqueous MeCN. Mechanistic Borderline between E2 and E1cb
  作者：Bong Rae Cho、Hyun Cheol Jeong、Yoon Je Seung、Sang Yong Pyun

  DOI：10.1021/jo025555m

  日期：2002.7.1

  Elimination reactions of 2-X-4-NO2C6H3CH2C(O)OC6H3-2-Y-4-NO2 [X = H (1), NO2 (2)] promoted by R2NH/R2NH2+ in 70 mol % MeCN(aq) have been studied kinetically. The base-promoted eliminations from 1 proceeded by the E2 mechanism when Y = Cl, CF3, and NO2. The mechanism changed to the competing E2 and E1cb mechanisms by the poorer leaving groups (Y = H, OMe) and to the E1cb extreme by the strongly electron-withdrawing

  在70 mol％MeCN（aq）中由R2NH / R2NH2 +促进的2-X-4- C6H3CH2C（O）OC6H3-2-Y-4-NO2 [X = H（1）， （2）]的消除反应已经完成动力学研究。当Y = Cl，CF3和 时，通过E2机制从1开始进行碱促消除。该机制由较差的离去基团（Y = H，OMe）变为竞争性的E2和E1cb机制，而由强吸电子的β-芳基（2，X = ）转变为E1cb极端。为消除1而计算出的beta = 0.14和beta（lg）= 0.10-0.21的值（Y = ）表示类似质子的过渡态，质子转移程度较小，Cα-OAr键断裂。离开的基团较差时，质子转移的程度增加，而离开的基团较弱时，离去基团键的裂解程度增加。也，k（1）和k（-1）/ k（2）值随反应物结构变化的变化与E1cb机制一致。根据这些结果，提出了从E2到E1cb极值机制转变的合理途径。
• Structure and Mechanism of PhnP, a Phosphodiesterase of the Carbon-Phosphorus Lyase Pathway
  作者：Shu-Mei He、Matthew Wathier、Kateryna Podzelinska、Matthew Wong、Fern R. McSorley、Alemayehu Asfaw、Bjarne Hove-Jensen、Zongchao Jia、David L. Zechel

  DOI：10.1021/bi2005398

  日期：2011.10.11

  PhnP is a phosphodiesterase that plays an important role within the bacterial carbon-phosphorus lyase (CP-lyase) pathway by recycling a “dead-end” intermediate, 5-phospho-α-d-ribosyl 1,2-cyclic phosphate, that is formed during organophosphonate catabolism. As a member of the metallo-β-lactamase superfamily, PhnP is most homologous in sequence and structure to tRNase Z phosphodiesterases. X-ray structural

  PhnP是一种磷酸二酯酶，通过回收“末端”中间体5-磷酸-α- d在细菌碳-磷裂解酶（CP-裂解酶）途径中发挥重要作用。-核糖基1,2-环磷酸酯，在有机膦酸酯分解代谢过程中形成。作为金属-β-内酰胺酶超家族的成员，PnP在序列和结构上与tRNase Z磷酸二酯酶最同源。用PhnP与原钒酸酯络合至1.5Å分辨率的X射线结构分析表明，该抑制剂在四面体几何结构中被两个催化锰离子和推定的一般酸残基H200结合。在这种结构的指导下，我们通过定点诱变，动力学分析和ICP-MS探索了第一和第二球活性位点残基对催化和金属离子结合的贡献。H200变为丙氨酸导致k cat / K M降低6–33倍带有取代的甲基苯基磷酸二酯，离去基团p K a的值在4至8.4之间。以双（对硝基苯基）磷酸酯为底物，k cat / K M降低了10倍，这主要是由于K M大大增加的结果。此外，镍离子活化的H200A PhnP对k cat
• Study on the Transesterification of Methyl Aryl Phosphorothioates in Methanol Promoted by Cd(II), Mn(II), and a Synthetic Pd(II) Complex
  作者：David R. Edwards、Alexei A. Neverov、R. Stan Brown

  DOI：10.1021/ic102220m

  日期：2011.3.7

  e-2C,N)palladium(II) (3), are shown to promote the methanolytic transesterification of O-methyl O-4-nitrophenyl phosphorothioate (2b) at 25 °C with impressive rate accelerations of 106−1011 over the background methoxide promoted reaction. A detailed mechanistic investigation of the methanolytic cleavage of 2a−d having various leaving group aryl substitutions, and particularly the 4-nitrophenyl derivative

  含有Cd（II），Mn（II）和palladacycle的甲醇溶液（二甲醇双（N，N-二甲基苄胺-2C，N）钯（II）（3）已显示可促进O-甲基的甲醇酯交换反应O -4-硝基苯基硫代磷酸酯（2b）在25°C时以10 -6 -10 11的惊人速率加速，超过了背景甲醇盐促进的反应，详细研究了具有各种离去基团芳基取代的2a - d的甲醇裂解，以及特别是Pd络合物3催化的4-硝基苯基衍生物（2b）被表达。的曲线图ķ OBS与钯环[ 3 ]表明强饱和结合以形成图2b：3。动力学数据与通用结合方程的数值拟合提供了2b：3配合物（k cat）的甲醇分解反应的结合常数K b和一阶催化速率常数，当对缓冲作用进行校正时，可以给出校正后的（k cat corr）速率常数。log（k cat corr）与s s的S形曲线图pH值（在甲醇中）用于裂解2b中显示了广阔的小号小号pH依赖性区域从5.6≤小号小号pH值≤〜10与ķ最小=（1
• Ketene-forming elimination reactions from aryl phenylacetates promoted by R2NH in MeCN: effects of base-solvent andβ-phenyl group
  作者：Sang Yong Pyun、Hyoun Jung Seok、Ju Chang Kim、Hwan Myung Kim、Bong Rae Cho

  DOI：10.1002/poc.1233

  日期：2007.9

  Elimination reactions of C6H5C(R)HCO2C6H3-2-X-4-NO2 [R = H (1), Ph (2), X = H (a), Cl (b), NO2 (c)] promoted by R2NH in MeCN have been studied kinetically. The reactions are second-order and exhibit Brönsted β = 0.46–0.89 and |βlg| = 0.37–0.76 and an E2 mechanism is evident. When the base-solvent was changed from R2NH/R2NH–70 mol% MeCN(aq) to R2NH-MeCN, β and |βlg| values remained nearly the same within

  C 6 H 5 C（R）HCO 2 C 6 H 3 -2-X-4-NO 2的消除反应[R = H（1），Ph（2），X = H（a），Cl（b）动力学研究了R 2 NH在MeCN中促进的NO 2（c）] 。的反应是二阶并且表现出布朗斯台德β  = 0.46-0.89和| β LG | = 0.37–0.76，并且有一个E2机制是明显的。当基础溶剂从R 2 NH / R 2 NH –70 mol％MeCN（aq）变为R 2时NH-MeCN，β和| β LG | 值在实验误差范围内几乎保持不变。对于1和2的消除，β和| β LG | 尽管β- Ph组抑制了该速率，但其值几乎相同。值得注意的是，形成烯酮的过渡态对碱溶剂和β - R基团变化的相对不敏感性。版权所有©2007 John Wiley＆Sons，Ltd.