2-(2,6-dimethylphenyl)thioxanthen-9-one | 193087-06-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 硫色烯
• 英文名称: 2-(2,6-dimethylphenyl)thioxanthen-9-one
• CAS: 193087-06-8
• 化学式: C₂₁H₁₆OS
• 分子量: 316.423
• InChiKey: UAVFFMQNBRQXIL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  23
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(2,6-dimethylphenyl)thioxanthen-9-one 在 tetraphosphorus decasulfide 作用下， 以 甲苯 为溶剂， 反应 0.17h， 以82%的产率得到2-(2,6-dimethylphenyl)thioxanthene-9-thione
  参考文献：
  名称：

  Toward a Switchable Molecular Rotor. Unexpected Dynamic Behavior of Functionalized Overcrowded Alkenes

  摘要：

  In an approach toward a photochemically bistable molecular rotor the Synthesis of cis-la and trans-1b isomers of 2-(2,6-dimethylphenyl)-9-(2',3'-dihydro-1'H-naphtho[2,1-b]thiopyran-1'-ylidene)-9H-thioxanthene (1), being sterically overcrowded alkenes functionalized with an o-xylyl group as a rotor, is described. The key steps in the synthesis are a Suzuki coupling to attach the xylyl moiety and a diazo-thioketone coupling with subsequent desulfurization to introduce the central olefinic bond in 1. The X-ray structure of cis-la revealed an anti-folded helical conformation. Dynamic NMR studies on both isomers were performed, to elucidate the kinetics of their rotation processes and to investigate the possibility to control the biaryl rotation by photochemical cis-trans isomerization. A rotation barrier was found by coalescence spectroscopy for cis-la: Delta G(c)(double dagger)=22 +/- 1 kcal mol(-1) in DMSO-d(6). 2D exchange spectroscopy (EXSY) showed barriers for cis-la: Delta G(303)(double dagger) 19.0 +/- 0.2 kcal mol(-1) and trans-1b: Delta G(303)(double dagger)=19.7 +/- 0.2 kcal mol(-1) in DMSO-d(6), respectively. Molecular mechanics and semiempirical calculations support the unexpected higher barrier for trans-lb. Since the rotation barriers are different for the cis and trans isomer, it can be concluded that control of a second mechanical effect, e.g. the rate of rotation of an attached biaryl rotor, is feasible in a photochemically switchable system.

  DOI：

  10.1021/jo962210t
• 作为产物：
  描述：

  2-氨基-9H-噻吨-9-酮 在 盐酸 、 barium dihydroxide 、 四(三苯基膦)钯 、 potassium iodide 、 sodium nitrite 作用下， 以 乙二醇二甲醚 为溶剂， 反应 18.25h， 生成 2-(2,6-dimethylphenyl)thioxanthen-9-one
  参考文献：
  名称：

  Toward a Switchable Molecular Rotor. Unexpected Dynamic Behavior of Functionalized Overcrowded Alkenes

  摘要：

  In an approach toward a photochemically bistable molecular rotor the Synthesis of cis-la and trans-1b isomers of 2-(2,6-dimethylphenyl)-9-(2',3'-dihydro-1'H-naphtho[2,1-b]thiopyran-1'-ylidene)-9H-thioxanthene (1), being sterically overcrowded alkenes functionalized with an o-xylyl group as a rotor, is described. The key steps in the synthesis are a Suzuki coupling to attach the xylyl moiety and a diazo-thioketone coupling with subsequent desulfurization to introduce the central olefinic bond in 1. The X-ray structure of cis-la revealed an anti-folded helical conformation. Dynamic NMR studies on both isomers were performed, to elucidate the kinetics of their rotation processes and to investigate the possibility to control the biaryl rotation by photochemical cis-trans isomerization. A rotation barrier was found by coalescence spectroscopy for cis-la: Delta G(c)(double dagger)=22 +/- 1 kcal mol(-1) in DMSO-d(6). 2D exchange spectroscopy (EXSY) showed barriers for cis-la: Delta G(303)(double dagger) 19.0 +/- 0.2 kcal mol(-1) and trans-1b: Delta G(303)(double dagger)=19.7 +/- 0.2 kcal mol(-1) in DMSO-d(6), respectively. Molecular mechanics and semiempirical calculations support the unexpected higher barrier for trans-lb. Since the rotation barriers are different for the cis and trans isomer, it can be concluded that control of a second mechanical effect, e.g. the rate of rotation of an attached biaryl rotor, is feasible in a photochemically switchable system.

  DOI：

  10.1021/jo962210t

文献信息

• Toward a Switchable Molecular Rotor. Unexpected Dynamic Behavior of Functionalized Overcrowded Alkenes
  作者：Anne Marie Schoevaars、Wim Kruizinga、Robert W. J. Zijlstra、Nora Veldman、Anthony L. Spek、Ben L. Feringa

  DOI：10.1021/jo962210t

  日期：1997.7.1

  In an approach toward a photochemically bistable molecular rotor the Synthesis of cis-la and trans-1b isomers of 2-(2,6-dimethylphenyl)-9-(2',3'-dihydro-1'H-naphtho[2,1-b]thiopyran-1'-ylidene)-9H-thioxanthene (1), being sterically overcrowded alkenes functionalized with an o-xylyl group as a rotor, is described. The key steps in the synthesis are a Suzuki coupling to attach the xylyl moiety and a diazo-thioketone coupling with subsequent desulfurization to introduce the central olefinic bond in 1. The X-ray structure of cis-la revealed an anti-folded helical conformation. Dynamic NMR studies on both isomers were performed, to elucidate the kinetics of their rotation processes and to investigate the possibility to control the biaryl rotation by photochemical cis-trans isomerization. A rotation barrier was found by coalescence spectroscopy for cis-la: Delta G(c)(double dagger)=22 +/- 1 kcal mol(-1) in DMSO-d(6). 2D exchange spectroscopy (EXSY) showed barriers for cis-la: Delta G(303)(double dagger) 19.0 +/- 0.2 kcal mol(-1) and trans-1b: Delta G(303)(double dagger)=19.7 +/- 0.2 kcal mol(-1) in DMSO-d(6), respectively. Molecular mechanics and semiempirical calculations support the unexpected higher barrier for trans-lb. Since the rotation barriers are different for the cis and trans isomer, it can be concluded that control of a second mechanical effect, e.g. the rate of rotation of an attached biaryl rotor, is feasible in a photochemically switchable system.