2-methyl-1-(tert-butylsulfinyl)naphthalene | 150587-82-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-methyl-1-(tert-butylsulfinyl)naphthalene
• 英文别名: 2-Methyl-1-(2-methyl-2-propylsulfinyl)naphthalene；1-Tert-butylsulfinyl-2-methylnaphthalene
• CAS: 150587-82-9
• 化学式: C₁₅H₁₈OS
• 分子量: 246.373
• InChiKey: PPHFMWKESPDTGS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  36.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-methyl-1-(tert-butylsulfinyl)naphthalene 在 间氯过氧苯甲酸 作用下， 生成 2-Methyl-1-(2-methylpropane-2-sulfonyl)naphthalene
  参考文献：
  名称：

  Atropisomerism in Hindered Naphthyl Sulfones Investigated by Dynamic NMR and Dynamic HPLC Techniques

  摘要：

  The existence of asymmetric conformations, leading to a pair of conformational enantiomers, has been observed by variable temperature NMR in hindered naphthyl sulfones, either monitoring the signals of prochiral groups or the signals of non-prochiral groups in a chiral environment. The corresponding enantiomerization barriers were determined by line shape analysis. In a sulfone featuring two stereogenic axes, the presence of both meso and racemic conformers has been detected and, by means of an appropriately cooled (-80 degrees C) enantioselective column, the three expected conformational stereoisomers have been physically separated, allowing assignment of the meso structure to the most stable species. MM calculations were also employed to describe the stereodynamic processes.

  DOI：

  10.1021/jo00122a034
• 作为产物：
  描述：

  1-溴-2-甲基萘 在 四(三苯基膦)钯 间氯过氧苯甲酸 作用下， 以 氯仿 、 水 、 正丁醇 为溶剂， 反应 7.0h， 生成 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

文献信息

• Baker, Robert W.; Kyasnoor, Rekha V.; Sargent, Melvyn V., Journal of the Chemical Society. Perkin Transactions 2 (2001), 1998, # 6, p. 1333 - 1337
  作者：Baker, Robert W.、Kyasnoor, Rekha V.、Sargent, Melvyn V.

  DOI：——

  日期：——
• Atropisomerism in Hindered Naphthyl Sulfones Investigated by Dynamic NMR and Dynamic HPLC Techniques
  作者：Daniele Casarini、Lodovico Lunazzi、Stefano Alcaro、Francesco Gasparrini、Claudio Villani

  DOI：10.1021/jo00122a034

  日期：1995.9

  The existence of asymmetric conformations, leading to a pair of conformational enantiomers, has been observed by variable temperature NMR in hindered naphthyl sulfones, either monitoring the signals of prochiral groups or the signals of non-prochiral groups in a chiral environment. The corresponding enantiomerization barriers were determined by line shape analysis. In a sulfone featuring two stereogenic axes, the presence of both meso and racemic conformers has been detected and, by means of an appropriately cooled (-80 degrees C) enantioselective column, the three expected conformational stereoisomers have been physically separated, allowing assignment of the meso structure to the most stable species. MM calculations were also employed to describe the stereodynamic processes.
• ACTINIC RAY-SENSITIVE OR RADIATION-SENSITIVE RESIN COMPOSITION, AND, ACTINIC RAY-SENSITIVE OR RADIATION-SENSITIVE FILM AND PATTERN FORMING METHOD, EACH USING THE SAME
  申请人：FUJIFILM Corporation

  公开号：US20140295332A1

  公开（公告）日：2014-10-02

  An actinic ray-sensitive or radiation-sensitive resin composition, which is excellent in sensitivity, resolution, a pattern profile and a depth of focus (DOF), and, an actinic ray-sensitive or radiation-sensitive film and a pattern forming method, each using the same, are provided. The actinic ray-sensitive or radiation-sensitive resin composition includes a nitrogen-containing compound and a resin (Ab) capable of varying a polarity or an alkali solubility thereof by the action of an acid.
• US9188862B2
  申请人：——

  公开号：US9188862B2

  公开（公告）日：2015-11-17
• Conformational studies by dynamic NMR. 50. Atropisomerism in hindered naphthyl sulfoxides: structure, stereodynamics, and chiral resolution
  作者：D. Casarini、E. Foresti、F. Gasparrini、L. Lunazzi、D. Misiti、D. Macciantelli、C. Villani

  DOI：10.1021/jo00073a028

  日期：1993.10

  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.