2-Methyl-1-(2-methyl-2-propylthio)naphthalene | 150587-85-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-Methyl-1-(2-methyl-2-propylthio)naphthalene
• 英文别名: 1-tert-butylsulfanyl-2-methylnaphthalene
• CAS: 150587-85-2
• 化学式: C₁₅H₁₈S
• 分子量: 230.374
• InChiKey: PEKQBTWLUGHPBE-UHFFFAOYSA-N

物化性质

• 沸点：
  339.7±21.0 °C(predicted)
• 密度：
  1.04±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.04
• 重原子数：
  16.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  2-Methyl-1-(2-methyl-2-propylthio)naphthalene 在 间氯过氧苯甲酸 作用下， 以 氯仿 、 水 为溶剂， 反应 1.0h， 以90%的产率得到2-methyl-1-(tert-butylsulfinyl)naphthalene
  参考文献：
  名称：

  Conformational studies by dynamic NMR. 50. Atropisomerism in hindered naphthyl sulfoxides: structure, stereodynamics, and chiral resolution

  摘要：

  Barriers for the EZ interconversion of atropisomers of 1-naphthyl sulfoxides (ArSOR) having a methyl group at position 2 of the naphthalene moiety were measured by variable-temperature NMR. Their values were found to cover the range 10.6-18.4 kcal mol-1, the extreme values corresponding to derivatives 1 (R = Me) and 4 (R = Bu(t)), respectively. NOE and LIS measurements indicated that the Z atropisomer is more stable than the E but that the absence of the methyl group at position 2 of the naphthalene moiety reverses this trend, rendering E more stable than Z. Solid-state NMR and X-ray diffraction of 4 established that only the more stable atropisomer (Z) is present in the crystalline state. Molecular mechanics calculations suggest that the Z,E interconversion process might occur by a rotation pathway having an opposite direction in the case of the more hindered derivatives 3 and 4 (R = Pr(i) and Bu(t), respectively) with respect to the less hindered 1 and 2 (R = Me and Et, respectively). The enantiomers, which are due to the presence of the asymmetric sulfur atom, were resolved on a chiral stationary phase (DACH-DNB) having an SS configuration. Asymmetric oxidation reactions were employed to assign the absolute R configuration to the more retained enantiomers of alkyl aryl sulfoxides. The opposite trend (S being retained longer) was observed for diaryl sulfoxides such as 5 (R = Ph). In the case of the derivative with the largest interconversion barrier, sulfoxide 4, it was also possible to resolve (at -35-degrees-C) the two enantiomeric forms and their associated atropisomers. The use of on-line CD detection and the knowledge of the NMR assignments allowed us to unambiguously assign the elution order of the four species as ES, ER, ZS, ZR.

  DOI：

  10.1021/jo00073a028
• 作为产物：
  描述：

  1-溴-2-甲基萘 、 2-甲基-2-丙硫醇钠盐 在 四(三苯基膦)钯 作用下， 以 正丁醇 为溶剂， 反应 6.0h， 以56%的产率得到2-Methyl-1-(2-methyl-2-propylthio)naphthalene
  参考文献：
  名称：

  Conformational studies by dynamic NMR. 50. Atropisomerism in hindered naphthyl sulfoxides: structure, stereodynamics, and chiral resolution

  摘要：

  Barriers for the EZ interconversion of atropisomers of 1-naphthyl sulfoxides (ArSOR) having a methyl group at position 2 of the naphthalene moiety were measured by variable-temperature NMR. Their values were found to cover the range 10.6-18.4 kcal mol-1, the extreme values corresponding to derivatives 1 (R = Me) and 4 (R = Bu(t)), respectively. NOE and LIS measurements indicated that the Z atropisomer is more stable than the E but that the absence of the methyl group at position 2 of the naphthalene moiety reverses this trend, rendering E more stable than Z. Solid-state NMR and X-ray diffraction of 4 established that only the more stable atropisomer (Z) is present in the crystalline state. Molecular mechanics calculations suggest that the Z,E interconversion process might occur by a rotation pathway having an opposite direction in the case of the more hindered derivatives 3 and 4 (R = Pr(i) and Bu(t), respectively) with respect to the less hindered 1 and 2 (R = Me and Et, respectively). The enantiomers, which are due to the presence of the asymmetric sulfur atom, were resolved on a chiral stationary phase (DACH-DNB) having an SS configuration. Asymmetric oxidation reactions were employed to assign the absolute R configuration to the more retained enantiomers of alkyl aryl sulfoxides. The opposite trend (S being retained longer) was observed for diaryl sulfoxides such as 5 (R = Ph). In the case of the derivative with the largest interconversion barrier, sulfoxide 4, it was also possible to resolve (at -35-degrees-C) the two enantiomeric forms and their associated atropisomers. The use of on-line CD detection and the knowledge of the NMR assignments allowed us to unambiguously assign the elution order of the four species as ES, ER, ZS, ZR.

  DOI：

  10.1021/jo00073a028