4-Hydroxy-2-(acetylamino)fluorene | 64724-49-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 4-Hydroxy-2-(acetylamino)fluorene
• 英文别名: N-2-<4-Hydroxy-fluorenyl>-acetamid；N-(4-Hydroxy-9H-fluoren-2-YL)acetamide
• CAS: 64724-49-8
• 化学式: C₁₅H₁₃NO₂
• 分子量: 239.274
• InChiKey: VWPRVEIEMCYNGL-UHFFFAOYSA-N

物化性质

• 熔点：
  270-272.5 °C (decomp)(Solv: methanol (67-56-1); water (7732-18-5))
• 沸点：
  535.0±50.0 °C(Predicted)
• 密度：
  1.330±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  49.3
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  重氮甲烷 、 4-Hydroxy-2-(acetylamino)fluorene 生成 4-Methoxy-2-(acetylamino)fluorene
  参考文献：
  名称：

  Nucleophilic substitution on the ultimate hepatacarcinogen N-(sulfonatooxy)-2-(acetylamino)fluorene by aromatic amines

  摘要：

  The kinetics and products of the reactions of the title compound 1 with aniline (5) and N,N-dimethylaniline (6) were investigated in MeOH. Addition of 5 (0.1-0.4 M) to a solution of 1 in MeOD-d4 has no effect on the overall rate of decomposition of 1 but generates a number of adducts (20-24) in moderate to high yield. The yields of all solvolysis products, except the rearranged O-sulfates 18 and 19, are suppressed by the addition of 5. The kinetic and product data are consistent with an S(N)1 mechanism (Scheme IV) in which 18 and 19 are generated by internal return from a tight ion pair, but all other products are generated by nucleophilic attack on a free nitrenium ion or solvent separated ion pair. The reaction of 6 with 1 shows similar characteristics to that of 5 with the exception that 6 reduces 1 in moderate yield to generate 2-(acetylamino)fluorene (25). This reduction occurs in competition with reaction to generate adducts (26, 27) similar to those obtained with 5. Kinetic and product data indicate that 25 is generated by reaction of 6 with a nitrenium ion intermediate. The differences in the behavior of 5 and 6 may be explained by cyclic voltammetry results which show that 6 is oxidized in MeOH more readily than 5 by about 2.5 kcal/mol. The reaction of 1 with 5 and 6 is considerably different from the reactions of the same amines with the N-aryl-O-pivaloylhydroxylamines, which were previously shown to proceed via an S(N)2 mechanism. This change in mechanism may be attributed, in part, to increased steric hindrance at the nitrogen of 1 due to the N-acetyl group.

  DOI：

  10.1021/jo00030a043
• 作为产物：
  描述：

  N-(Sulfonatooxy)-2-(acetylamino)fluorene 以 水 、 乙腈 为溶剂， 生成 4-Hydroxy-2-(acetylamino)fluorene 、 3-Chlor-2-acetamidofluoren 、
  参考文献：
  名称：

  Hydrolysis kinetics of the ultimate hepatacarcinogen N-(sulfonatooxy)-2-(acetylamino)fluorene: detection of long-lived hydrolysis intermediates

  摘要：

  DOI：

  10.1021/ja00194a072

文献信息

• Involvement of Free Nitrenium Ions, Ion Pairs, and Preassociation Trapping in the Reactions of Ester Derivatives of N-Arylhydroxylamines and N-Arylhydroxamic Acids in Aqueous Solution
  作者：Michael Novak、Mary Jo Kahley、Jing Lin、Sonya A. Kennedy、Tishia G. James

  DOI：10.1021/jo00130a034

  日期：1995.12

  Rate and product yield data for the decomposition of the ester derivatives of N-arylhydroxylamines and N-arylhydroxamic acids 1a-i in aqueous solution in the presence of N-3(-) support a mechanistic scheme (Scheme 5) in which the trapping by N-3(-) changes from trapping of the free ion, to trapping of an ion pair, to a preassociation process as the ion becomes more reactive. When the rate constant for trapping of the free ion by solvent, k(s), < similar to 10(8) s(-1), trapping by both N-3(-) and solvent occurs almost exclusively at the free ion. When 10(8) s(-1) < similar to k(s) < similar to 10(10) s(-1), a change in the mechanism occurs, and trapping of the ion pair by both solvent and N-3(-) becomes important. In this range of reactivity there is also evidence, based on the apparent magnitude of k(az)', the rate constant for N-3(-) trapping of the ion pair, that some of the reaction with N-3(-) occurs though a preassociation process. When k(s) > similar to 10(10) s(-1) essentially all of the observed N-3(-) trapping occurs by a preassociation process because N-3(-), which cannot react with the ion pair faster than the diffusion limit, can no longer compete with solvent for the ion pair. This progression in trapping mechanisms as the ion becomes more reactive with solvent is apparently an important factor in determining the carcinogenic potential of aromatic amines and amides which are metabolized into sulfuric and carboxylic acid esters of N-arylhydroxylamines and N-arylhydroxamic acids. Nitrenium ions that undergo slow reactions with solvent are selectively trapped by biologically relevant nucleophiles such as 2'-deoxyguanosine, As the rate constant for reaction with solvent increases, the nitrenium ion is no longer capable of undergoing selective trapping by nonsolvent nucleophiles because these reactions are rate limited by diffusion, but solvent trapping is not.
• Nucleophilic substitution on the ultimate hepatacarcinogen N-(sulfonatooxy)-2-(acetylamino)fluorene by aromatic amines
  作者：Michael Novak、Kanchugarakoppal S. Rangappa

  DOI：10.1021/jo00030a043

  日期：1992.2

  The kinetics and products of the reactions of the title compound 1 with aniline (5) and N,N-dimethylaniline (6) were investigated in MeOH. Addition of 5 (0.1-0.4 M) to a solution of 1 in MeOD-d4 has no effect on the overall rate of decomposition of 1 but generates a number of adducts (20-24) in moderate to high yield. The yields of all solvolysis products, except the rearranged O-sulfates 18 and 19, are suppressed by the addition of 5. The kinetic and product data are consistent with an S(N)1 mechanism (Scheme IV) in which 18 and 19 are generated by internal return from a tight ion pair, but all other products are generated by nucleophilic attack on a free nitrenium ion or solvent separated ion pair. The reaction of 6 with 1 shows similar characteristics to that of 5 with the exception that 6 reduces 1 in moderate yield to generate 2-(acetylamino)fluorene (25). This reduction occurs in competition with reaction to generate adducts (26, 27) similar to those obtained with 5. Kinetic and product data indicate that 25 is generated by reaction of 6 with a nitrenium ion intermediate. The differences in the behavior of 5 and 6 may be explained by cyclic voltammetry results which show that 6 is oxidized in MeOH more readily than 5 by about 2.5 kcal/mol. The reaction of 1 with 5 and 6 is considerably different from the reactions of the same amines with the N-aryl-O-pivaloylhydroxylamines, which were previously shown to proceed via an S(N)2 mechanism. This change in mechanism may be attributed, in part, to increased steric hindrance at the nitrogen of 1 due to the N-acetyl group.
• Hydrolysis kinetics of the ultimate hepatacarcinogen N-(sulfonatooxy)-2-(acetylamino)fluorene: detection of long-lived hydrolysis intermediates
  作者：Markandeswar Panda、Michael Novak、Jozef Magonski

  DOI：10.1021/ja00194a072

  日期：1989.6