(+)-(S)-1-methyl-5-nitroindene | 111466-86-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚和异茚
• 英文名称: (+)-(S)-1-methyl-5-nitroindene
• CAS: 111466-86-5
• 化学式: C₁₀H₉NO₂
• 分子量: 175.187
• InChiKey: WUUUSVTZPSFHKA-ZETCQYMHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.73
• 重原子数：
  13.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  43.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (+)-(S)-1-methyl-5-nitroindene 在 三乙烯二胺 作用下， 以 邻二氯苯 为溶剂， 生成 6-nitro-3-methylindene
  参考文献：
  名称：

  1,3-Hydron Transfer in Some 5- or 7-Substituted 1-Methylindenes. Reaction Rates and Kinetic Isotope Effects.

  摘要：

  Rate constants and primary deuterium kinetic isotope effects (KIEs) have been determined for the base-catalysed 1,3-hydrotropic rearrangements of 1-methyl-5-nitroindene (12), 1-methyl-7-nitroindene (13), 5-methoxy-1-methylindene (14) and 5-fluoro-1-methylindene (15) in o-dichlorobenzene at 20 degrees C. The tertiary amine 1,4-diazabicyclo [2.2.2]octane( DABCO) was used as catalyst. The kinetics were followed by polarimetry using the isotopic quasi-racemate method. The rearrangement of 13 was also investigated by H-1 NMR kinetic experiments. The reaction rate correlates, as expected, with the electronic effect of the substituent ranging from a large increase for the 5-nitro substrate to a small decrease for the methoxy compound as compared with the unsubstituted 1-methylindene. The KIEs vary as predicted from the Melander-Westheimer postulate showing an increase with reaction rate from 5.57 to 8.56. The syntheses of the (+)-(S)-form of the 5- or 7-substituted indenes and the (-)-(R)-form of the deuteriated analogues are also reported.

  DOI：

  10.3891/acta.chem.scand.52-0911
• 作为产物：
  描述：

  (S)-3-methyl-6-nitroindan-1-one 在 sodium tetrahydroborate 、 对甲苯磺酸 作用下， 以 甲醇 、 苯 为溶剂， 反应 3.5h， 生成 (+)-(S)-1-methyl-5-nitroindene
  参考文献：
  名称：

  1,3-Hydron Transfer in Some 5- or 7-Substituted 1-Methylindenes. Reaction Rates and Kinetic Isotope Effects.

  摘要：

  Rate constants and primary deuterium kinetic isotope effects (KIEs) have been determined for the base-catalysed 1,3-hydrotropic rearrangements of 1-methyl-5-nitroindene (12), 1-methyl-7-nitroindene (13), 5-methoxy-1-methylindene (14) and 5-fluoro-1-methylindene (15) in o-dichlorobenzene at 20 degrees C. The tertiary amine 1,4-diazabicyclo [2.2.2]octane( DABCO) was used as catalyst. The kinetics were followed by polarimetry using the isotopic quasi-racemate method. The rearrangement of 13 was also investigated by H-1 NMR kinetic experiments. The reaction rate correlates, as expected, with the electronic effect of the substituent ranging from a large increase for the 5-nitro substrate to a small decrease for the methoxy compound as compared with the unsubstituted 1-methylindene. The KIEs vary as predicted from the Melander-Westheimer postulate showing an increase with reaction rate from 5.57 to 8.56. The syntheses of the (+)-(S)-form of the 5- or 7-substituted indenes and the (-)-(R)-form of the deuteriated analogues are also reported.

  DOI：

  10.3891/acta.chem.scand.52-0911

文献信息

• 1,3-Hydron transfer in some 5- and 7-substituted 1-methylindenes. Enantioselectivities and enantiomer-dependent kinetic isotope effects
  作者：Marie Aune、G�ran Bergson、Olle Matsson

  DOI：10.1002/poc.610080604

  日期：1995.6

  [5-methoxy- (2), 5-fluoro- (3), 5-nitro- (4) and 7-nitro (5)] and 1-methylindene (1) were employed as substrates. The rate constants, the enantioselectivities and the kinetic isotope effects (KIEs) for the enantioselective reactions [(kH/kD)+ and (kH/kD)−] were determined at 20°C using (+)-(8R, 9S)-dihydroquinidine as chiral catalyst in the solvent o-dichlorobenzene. The rate constants vary according to the

  在茚体系中研究了碱催化的底物-对映选择性的1，3-氢转移（动力学拆分）。在芳香环中取代的一系列1-甲基茚[5-甲氧基-（2），5-氟-（3），5-硝基-（4）和7-硝基（5）]和1-甲基茚（1）被用作底物。对映选择性反应[（k H / k D）+和（k H / k D）- ]的速率常数，对映选择性和动力学同位素效应（KIEs）在20°C下使用（+）-（8 R，9 S）-二氢奎尼丁为溶剂o的手性催化剂-二氯苯。速率常数根据取代基的电子效应而变化。初级氘KIE范围从4·73 [对于（+）-（S）-2]到11·3 [对于（-）-（R）-5]，与速率常数相关，如预期的那样Melander–Westheimer假设。在芳环中引入取代基降低了对映选择性。除了5中的所有化合物显示的对映选择性的同样的意义[ ķ + / ķ - > 1; 使用的所有底物均为（+）-（S）/（-）-（R）]。KIE的对映异构体依赖性在1