[S(S)]-4-bromo-3,3,6,6-tetramethoxy-1-p-tolylsulfinyl-1,4-cyclohexadiene | 943136-50-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [S(S)]-4-bromo-3,3,6,6-tetramethoxy-1-p-tolylsulfinyl-1,4-cyclohexadiene
• CAS: 943136-50-3
• 化学式: C₁₇H₂₁BrO₅S
• 分子量: 417.321
• InChiKey: VDNUFOKKLFNUFG-DEOSSOPVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.26
• 重原子数：
  24.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  53.99
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  [S(S)]-4-bromo-3,3,6,6-tetramethoxy-1-p-tolylsulfinyl-1,4-cyclohexadiene 在 ammonium cerium(IV) nitrate 作用下， 以 氘代氯仿 、 乙腈 为溶剂， 反应 72.0h， 生成 [S(S)]-5-bromo-2'-trifluoromethyl-4-methoxy-2-p-tolylsulfinylazobenzene
  参考文献：
  名称：

  Photoinduced Conformational Switch of Enantiopure Azobenzenes Controlled by a Sulfoxide

  摘要：

  Two series of enantiopure azobenzenes with a p-tolylsulfoxide at the ortho or meta position with respect to the azo group, have been regioselectively synthesized. Both can act as enantiopure molecular switches showing different structural features owing to the presence of the stereogenic sulfur. The photoisomerization process, studied by UV-vis, circular dichroism (CD), NMR, and chiral HPLC evidenced a double role of the sulfoxide. A transfer of chirality from the sulfoxide to the azo system was observed by CD in both cis and trans-isomers of the meta sulfinyl derivatives 3, whereas this perturbation was evident for the ortho sulfinyl series 7 only in the cis isomer. The NMR study evidenced that the s-cis rigid conformation of the bisaromatic sulfoxide was fixing a different orientation of the overall system in each series both in the trans and cis isomers, by forcing a final U-shaped structure in cis-3 and an S-shaped structure in cis-7. Very different values of specific optical rotations were measured in both trans and cis isomers, also reflecting the existence of distinct chiral entities in the photostationary states. The easy and reversible changes occurring between different conformational states could find applications in the photocontrol of several molecular switches.

  DOI：

  10.1021/ja070163o
• 作为产物：
  描述：

  甲醇 、 [S(S)]-5-bromo-1,4-dimethoxy-2-(p-tolylsulfinyl)benzene 在 platinum on activated charcoal 氢氧化钾 作用下， 反应 2.0h， 以90%的产率得到[S(S)]-4-bromo-3,3,6,6-tetramethoxy-1-p-tolylsulfinyl-1,4-cyclohexadiene
  参考文献：
  名称：

  Photoinduced Conformational Switch of Enantiopure Azobenzenes Controlled by a Sulfoxide

  摘要：

  Two series of enantiopure azobenzenes with a p-tolylsulfoxide at the ortho or meta position with respect to the azo group, have been regioselectively synthesized. Both can act as enantiopure molecular switches showing different structural features owing to the presence of the stereogenic sulfur. The photoisomerization process, studied by UV-vis, circular dichroism (CD), NMR, and chiral HPLC evidenced a double role of the sulfoxide. A transfer of chirality from the sulfoxide to the azo system was observed by CD in both cis and trans-isomers of the meta sulfinyl derivatives 3, whereas this perturbation was evident for the ortho sulfinyl series 7 only in the cis isomer. The NMR study evidenced that the s-cis rigid conformation of the bisaromatic sulfoxide was fixing a different orientation of the overall system in each series both in the trans and cis isomers, by forcing a final U-shaped structure in cis-3 and an S-shaped structure in cis-7. Very different values of specific optical rotations were measured in both trans and cis isomers, also reflecting the existence of distinct chiral entities in the photostationary states. The easy and reversible changes occurring between different conformational states could find applications in the photocontrol of several molecular switches.

  DOI：

  10.1021/ja070163o