N-(4'-Aminophenyl)-2-(acetylamino)fluorene | 138235-75-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: N-(4'-Aminophenyl)-2-(acetylamino)fluorene
• 英文别名: N-(4-aminophenyl)-N-(9H-fluoren-2-yl)acetamide
• CAS: 138235-75-3
• 化学式: C₂₁H₁₈N₂O
• 分子量: 314.387
• InChiKey: NCEVMWYZWMTNMS-UHFFFAOYSA-N

物化性质

• 沸点：
  643.5±48.0 °C(Predicted)
• 密度：
  1.263±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  46.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  [acetyl(9H-fluoren-3-yl)amino] 2,2-dimethylpropanoate 、 苯胺 、 甲醇 以17%的产率得到
  参考文献：
  名称：

  Novak Michael, Rangappa Kanchugarakoppal, Manitsas Rebecca K., J. Org. Chem, 58 (1993) N 27, S 7813- 7821

  摘要：

  DOI：

文献信息

• Nucleophilic aromatic substitution on ester derivatives of carcinogenic N-arylhydroxamic acids by aniline and N,N-dimethylaniline
  作者：Michael Novak、Kanchugarakoppal S. Rangappa、Rebecca K. Manitsas

  DOI：10.1021/jo00079a028

  日期：1993.12

  Decomposition of N-(pivaloyloxy)-2-(acetylamino)fluorene (1b) and N-(sulfonatooxy)-4-(acetylamino)-biphenyl (2a) in MeOH occurs predominately via N-0 bond cleavage to yield oxazoles (5, 6, 23), methoxy adducts (7,8,24,25,26), and rearrangement products (10b,11b,28). Minor ester methanolysis paths lead to the N-arylhydroxamic acids (9, 27). In the presence of 0.1 M aniline (3), 1b yields a number of adducts (14-18) identical to those previously obtained from the reaction of 3 with N-(sulfonatooxy)-2-(acetylamino)fluorene (1a). This occurs with no change in the rate constant for decomposition of 1b. At 0.1 M 3 all solvolysis products of 1b, except the rearrangement products 10 band 11b, are reduced below detectable levels. Similar results were obtained for 2a, which yields the adducts 30-35 in the presence of 3 and 36-38 in the presence of N,N-dimethylaniline (4). These results are consistent with a mechanism (Scheme V) in which the N-O bond heterolysis leads to a tight ion pair that can undergo internal return to yield the rearrangement products or diffusional separation to yield the free ion. The free nitrenium ion can be trapped by solvent or added nucleophiles. Both the N-acetyl-N-(4-biphenylyl)nitrenium ion (45) and the N-acetyl-N-(2-fluorenyl)nitrenium ion (48) react slowly enough with the solvent to undergo selective reaction with strong nucleophiles. Since 1a, 1b, and 2a span the reactivity range of the ester derivatives of the common N-arylhydroxamic acids which undergo N-O bond heterolysis in H2O, it appears that all of the carcinogenic esters will react with simple aromatic amines via an S(N)1 mechanism.
• 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.