2-(2,6-dimethylphenyl)thioxanthene-9-thione | 193087-07-9

• 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)thioxanthene-9-thione
• CAS: 193087-07-9
• 化学式: C₂₁H₁₆S₂
• 分子量: 332.49
• InChiKey: BPXCMDIIDSWHKD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 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：
  57.4
• 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)thioxanthene-9-thione 在 甲醇 、 氢氧化钾 、 magnesium sulfate 、 silver(l) oxide 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以31%的产率得到dispiro[2,3-dihydro-1H-naphtho[2,1-b]pyran-1,2'-thiirane-3',9''-[2''-(2,6-dimethylphenyl)-9''H-thioxanthene]]
  参考文献：
  名称：

  Fine tuning of molecular rotor function in photochemical molecular switches

  摘要：

  Molecular switches are used as scaffolds for the construction of controlled molecular rotors. The internal position of the switching entity in the molecule controls the dynamic behaviour of the rotor moiety in the molecule. Six new molecular motors with o-xylyl rotor moieties were prepared on the basis of an overcrowded alkene, and their dynamics were systematically studied by 2D EXSY NMR, Variation of the (hetero-)atoms in the upper and lower halves of the overcrowded alkene allows fine tuning of the rate of rotation of the o-xylyl rotor in the lower half of the molecule. For all rotors it was observed that the rotation barrier for the trans-isomer was higher than that of the corresponding cis-isomer. The results are analyzed and discussed in terms of differences in steric interactions in the presented system. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2009.03.081
• 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 、 tetraphosphorus decasulfide 、 potassium iodide 、 sodium nitrite 作用下， 以 乙二醇二甲醚 、 甲苯 为溶剂， 反应 18.42h， 生成 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

文献信息

• Control of rotor motion in a light-driven molecular motor: towards a molecular gearbox
  作者：Matthijs K. J. ter Wiel、Richard A. van Delden、Auke Meetsma、Ben L. Feringa

  DOI：10.1039/b510641a

  日期：——

  Controlled intramolecular movement and coupling of motor and rotor functions is exerted by this new molecular device. The rate of rotation of the rotor part of the molecule can be adjusted by alteration of the conformation of the motor part of the molecule. For all states of the motor part, different rates of rotation were measured for the rotor part. Conversion between the four propeller orientations was achieved by irradiation and heating.

  这种新的分子装置可以控制分子内的运动以及马达和转子功能的耦合。分子转子部分的旋转速率可以通过改变分子马达部分的构象来调节。在马达部分的所有状态下，都测得了转子部分的不同旋转速率。四种螺旋桨方向之间的转换是通过辐照和加热实现的。
• Fine tuning of molecular rotor function in photochemical molecular switches
  作者：Matthijs K.J. ter Wiel、Ben L. Feringa

  DOI：10.1016/j.tet.2009.03.081

  日期：2009.5

  Molecular switches are used as scaffolds for the construction of controlled molecular rotors. The internal position of the switching entity in the molecule controls the dynamic behaviour of the rotor moiety in the molecule. Six new molecular motors with o-xylyl rotor moieties were prepared on the basis of an overcrowded alkene, and their dynamics were systematically studied by 2D EXSY NMR, Variation of the (hetero-)atoms in the upper and lower halves of the overcrowded alkene allows fine tuning of the rate of rotation of the o-xylyl rotor in the lower half of the molecule. For all rotors it was observed that the rotation barrier for the trans-isomer was higher than that of the corresponding cis-isomer. The results are analyzed and discussed in terms of differences in steric interactions in the presented system. (C) 2009 Elsevier Ltd. All rights reserved.
• 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.