2,10-bis(methylthio)-8,16-diformyl-[2.2]metacyclophane | 1266185-40-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,10-bis(methylthio)-8,16-diformyl-[2.2]metacyclophane
• CAS: 1266185-40-3
• 化学式: C₂₀H₂₀O₂S₂
• 分子量: 356.51
• InChiKey: RCVMMKRUBHMGNZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.92
• 重原子数：
  24.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  34.14
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2,10-bis(methylthio)-8,16-diformyl-[2.2]metacyclophane 在 potassium tert-butylate 作用下， 以 四氢呋喃 、 二氯甲烷 、 氘代甲苯 为溶剂， 反应 5.33h， 生成 10b,10c-bis((1E)-2-phenylvinyl)-trans-10b,10c-dihydropyrene
  参考文献：
  名称：

  Syntheses of Dihydropyrene–Cyclophanediene Negative Photochromes Containing Internal Alkenyl and Alkynyl Groups and Comparison of Their Photochemical and Thermochemical Properties

  摘要：

  Synthesis of a variety of 8,16-disubstituted-anti-[2.2]-metacyclophanedienes (CPD) with alkenyl and allcynyl internal (8,16) groups is described together with their analogous dihydropyrenes (DHP). Eyring and Arrhenius parameters were determined for the thermal closing reaction, CPD to DHP, and half-lives at 20 degrees C were found to range from 11 days (X = CHO) to 36 years (X = CN), with alkenyl functions being from 56 days to 10 years. The visible light opening reaction, DHP to CPD, showed relative rates of 1 (X = CN) to 240 (X = CH=CMe2).

  DOI：

  10.1021/jo4024446
• 作为产物：
  描述：

  2,9-Bis(methylsulfanyl)tricyclo[9.3.1.14,8]hexadeca-1(14),4(16),5,7,11(15),12-hexaene-15,16-dicarbonitrile 在 二异丁基氢化铝 、 甲醇 、 盐酸 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 4.0h， 以88%的产率得到2,10-bis(methylthio)-8,16-diformyl-[2.2]metacyclophane
  参考文献：
  名称：

  Calculation Driven Synthesis of an Excellent Dihydropyrene Negative Photochrome and its Photochemical Properties

  摘要：

  The photochromic properties of dihydropyrenes have been substantially improved by making use of density functional theory (DFT) activation barrier calculations, which suggested that the di-isobutenylcyclophanediene 15' should have a significant barrier to thermal isomerization to the dihydropyrene (DHP) 15, which itself should resist isomerization involving migration of the internal groups to the rearranged dihydropyrene 9 (X = -CH=C(Me)(2)). As a result of these calculations, the synthesis of the colorless cyclophanediene (CPD) 15' was undertaken and achieved from the dinitrile 28 in four steps in 37% overall yield %. The cyclophanediene 15' thermally isomerized to the dihydropyrene 15 at 100 degrees C with t(1/2) = 4.5 h, giving an extrapolated 20 degrees C t(1/2) of similar to 16 y, consistent with the DFT calculations. No evidence for [1,5]-sigmatropic rearrangement in to 9 (X = -CH=C(Me)(2)) was observed on heating to 130 degrees C. The ring-opening isomerization quantum yields (phi(open)) for DHP 15 in to CPD 15' were determined in cyclohexane to be 0.12 +/- 0.01, which is three times greater than for the benzoDHP 1. Friedel-Crafts naphthoylation of 15 gave 70% of purple 32, which in toluene showed the largest photochemical ring-opening isomerization quantum yields (phi(open)) of 0.66 +/- 0.02 for any known dihydropyrene, similar to nine times greater than 1 in toluene. The thermal closing of 32' to 32, although faster than for 15', gave a useful extrapolated t(1/2) of similar to 2 y at 20 degrees C.

  DOI：

  10.1021/ja1100596