2,5-di(4-methoxyphenyl)-1,4-dithiin | 37989-51-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2,5-di(4-methoxyphenyl)-1,4-dithiin
• 英文别名: 2,5-bis-(4-methoxy-phenyl)-[1,4]dithiine；2,5-bis(4-anisyl)-1,4-dithiin；2,5-di(p-methoxyphenyl)dithiin；2,5-Bis(4-methoxyphenyl)-1,4-dithiine
• CAS: 37989-51-8
• 化学式: C₁₈H₁₆O₂S₂
• 分子量: 328.456
• InChiKey: XTCLQKGOKJVVKQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  69.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,5-di(4-methoxyphenyl)-1,4-dithiin 在 2,6-二甲基吡啶 、 tert-butylammonium hexafluorophosphate(V) 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 以22%的产率得到3,6,3',6'-Tetrakis-(4-methoxy-phenyl)-[2,2']bi[[1,4]dithiinyl]
  参考文献：
  名称：

  The Dimerization of 2,5-Diaryl-1,4-dithiin Radical Cations.

  摘要：

  The electrochemical oxidation of five 2,5-diaryl-1,4-dithiins with aryl=p-anisyl (BAD), p-tolyl (BTD), phenyl (DPD), p-chlorophenyl (BCD) and p-nitrophenyl (END) has been studied in MeCN-CH2Cl2 (1:1) by cyclic voltammetry (CV), derivative cyclic voltammetry (DCV) and linear sweep voltammetry (LSV) as well as constant current coulometry and product analyses. All compounds were found to undergo two quasi-reversible one-electron transfers to the radical cations and the dications. The formal potential of the first redox couple and the life-time of the radical cation were found to decrease when the aryl group became more electron donating. The radical cation of END was non-reactive on the timescale of slow-scan CV, whereas the radical cation of BAD was so reactive that it was impossible to outrun the follow-up reaction even at a scan rate of 1000 V s(-1). The number of electrons determined in the presence of 2,6-lutidine, added to prevent acid-catalyzed conversion of substrate, was between 1.1 and 1.5 except for END, the radical cation of which catalyzed the oxidation of some unknown species in the solution. The major products from preparative electrolysis were the corresponding 2,2'-dimers, which were isolated in yields up to 20%. A detailed mechanistic and kinetic analysis of the dimerization, in the presence of 2,6-lutidine, involving the simultaneous fitting of theoretical data and experimental data obtained by LSV and DCV on a timescale covering several orders of magnitude, demonstrated that the process was of the radical cation-radical cation type and allowed for the determination of rate and equilibrium constants, k(1) and K-1. In addition, the values of the heterogeneous electron transfer rate constant, k(8), and the transfer coefficient, alpha, could be determined this way. The values of k(1) were found to vary between 2.2x10(6) M(-1) s(-1) (BAD) and 8.7 x 10(2) M(-1) s(-1) (BCD). The Hammett-plot, log k(1) vs. sigma(+), was linear indicating the importance of resonance stabilization for the dicationic transition state. The formal potentials for the reversible oxidation of the 2,2'-dimers to the radical cations were 70-120 mV higher than those for the monomers although AMI calculations predicted the ionization potentials of the dimers to be slightly lower than those for monomers. It is suggested that differences in solvation more than counterbalance the purely electronic effects.

  DOI：

  10.3891/acta.chem.scand.51-0094
• 作为产物：
  描述：

  4-[2-(4-methoxyphenyl)-2-oxoethyl]sulfanyl-1H-quinazolin-2-one 以60%的产率得到
  参考文献：
  名称：

  SINGH, HARJIT, AGGARWAL, SUNIL, K.;MALHOTRA, NAGESHWAR, HETEROCYCLES, 1983, 20, N 6, 983-984

  摘要：

  DOI：

文献信息

• Disproportionation of rosin in the presence of dithiin derivatives
  申请人：Hercules Incorporated

  公开号：US04265807A1

  公开（公告）日：1981-05-05

  Disclosed is a method of disproportionating rosin comprising heating said rosin in the presence of a dithiin derivative such, for example, as 2,5-diphenyl dithiin. The method can be carried out at about 150.degree. C. to about 300.degree. C. for about 1 hour to about 10 hours with the longer reaction time corresponding to the lower temperatures. Preferably, the process is run at about 260.degree. C. to about 300.degree. C. for about 3 to 8 hours.

  揭示了一种松香不均化的方法，包括在存在二硫代烯衍生物的情况下加热所述松香，例如2,5-二苯基二硫代烯。该方法可在大约150°C至大约300°C的温度下进行，反应时间约为1小时至10小时，较长的反应时间对应较低的温度。最好在大约260°C至大约300°C的温度下进行约3至8小时的过程。
• SKELETAL REARRANGEMENT OF 2,5-DIARYL-1,4-DITHIIN-1-OXIDES INDUCED BY HYDROCHLORIC ACID
  作者：Keiji Kobayashi、Kiyoshi Mutai

  DOI：10.1246/cl.1981.1105

  日期：1981.8.5

  Treatment of 2,5-diphenyl-1,4-dithiin-1-oxide with hydrochloric acid in dioxane caused a novel skeletal rearrangement to give 2-benzoyl-4-phenyl-1,3-dithiole together with the deoxygenation products. The reaction with gaseous hydrogen chloride in methanol afforded the adduct due to the additive Pummerer rearrangement, which was also converted into the 1,3-dithiole.

  用盐酸在二恶烷中处理 2,5-diphenyl-1,4-dithiin-1-oxide 导致新的骨架重排，生成 2-benzoyl-4-phenyl-1,3-dithiole 和脱氧产物。与气态氯化氢在甲醇中的反应由于加成的普默勒重排而得到加合物，它也被转化为 1,3-二硫醇。
• Rhodium-Catalyzed Isomerization and Alkyne Exchange Reactions of 1,4-Dithiins via the 1,2-Ethenedithiolato Rhodium Complex
  作者：Mieko Arisawa、Kyosuke Sawahata、Takuya Ichikawa、Masahiko Yamaguchi

  DOI：10.1021/acs.organomet.8b00498

  日期：2018.9.24

  Rhodium-catalyzed isomerization and alkyne exchange reactions of 1,4-dithiines occurred by cleavage of two C–S bonds. The 2,5- and 2,6-disubstituted 1,4-dithiins underwent isomerization reactions in toluene at 110 °C, providing equilibrium mixtures of isomers. At 150 °C, the reaction of 1,4-dithiins and dimethyl acetylenedicarboxylate gave unsymmetric 2,3-di(methoxycarbonyl)-1,4-dithiins and 2,3-d

  铑催化的1，4-二乙酮的异构化和炔烃交换反应是通过两个C-S键的断裂而发生的。2，5-和2，6-二取代的1，4-二硫辛在甲苯中于110°C进行异构化反应，提供了异构体的平衡混合物。在150°C下，1,4-二硫辛和乙炔二羧酸二甲酯反应生成不对称的2,3-二（甲氧羰基）-1,4-二硫辛和2,3-二（甲氧羰基）噻吩，后者是由1,4-二硫精脱硫。炔烃和1，2-二硫杂环丁烷的相关反应得到2，3-二（甲氧基羰基）噻吩。这些反应被认为涉及1，2-乙二硫醇基铑中间体。
• Singh, Harjit; Aggarwal, Sunil K.; Malhotra, Nageshwar, Heterocycles, 1983, vol. 20, # 6, p. 983 - 984
  作者：Singh, Harjit、Aggarwal, Sunil K.、Malhotra, Nageshwar

  DOI：——

  日期：——
• Extrusion reactions-VII
  作者：Harjit Singh、Sunil K. Aggarwal、Nageshwar Malhotra

  DOI：10.1016/s0040-4020(01)91330-4

  日期：1984.1