1,1'-(phenylenedioxydiethylene)dithymine | 160148-58-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1,1'-(phenylenedioxydiethylene)dithymine
• 英文别名: 5-Methyl-1-[2-[2-[2-(5-methyl-2,4-dioxopyrimidin-1-yl)ethoxy]phenoxy]ethyl]pyrimidine-2,4-dione；5-methyl-1-[2-[2-[2-(5-methyl-2,4-dioxopyrimidin-1-yl)ethoxy]phenoxy]ethyl]pyrimidine-2,4-dione
• CAS: 160148-58-3
• 化学式: C₂₀H₂₂N₄O₆
• 分子量: 414.418
• InChiKey: WWVXVQIWTQHWKR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  30
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  117
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,1'-(phenylenedioxydiethylene)dithymine 在 苯乙酮 作用下， 以 水 、 乙腈 为溶剂， 生成 trans-syn-1,8-(1,2phenylenedioxydiethylene)hexahydro-4a,4b-dimethylcyclobuta<1,2-d:4,3-d'>dipyrimidine-2,4,5,7(3H,6H)-tetrone
  参考文献：
  名称：

  合成和透视新颖的晶体结构的反式-顺式胸腺嘧啶photodimers：上photodimer立体化学聚氧乙烯间隔链的效果

  摘要：

  反式-顺式二聚体1和2的X射线晶体结构已经确定，它们是双胸腺嘧啶光二聚化后的唯一产物。

  DOI：

  10.1039/c39940002275
• 作为产物：
  描述：

  1,2-双(2-溴乙氧基)苯 、 胸腺嘧啶 在 三甲基氯硅烷 、 六甲基二硅氮烷 作用下， 生成 1,1'-(phenylenedioxydiethylene)dithymine
  参考文献：
  名称：

  合成和透视新颖的晶体结构的反式-顺式胸腺嘧啶photodimers：上photodimer立体化学聚氧乙烯间隔链的效果

  摘要：

  反式-顺式二聚体1和2的X射线晶体结构已经确定，它们是双胸腺嘧啶光二聚化后的唯一产物。

  DOI：

  10.1039/c39940002275

文献信息

• Synthesis and X-ray crystal structure of novel trans-syn thymine photodimers: effect of a polyoxyethylene spacer chain on photodimer stereochemistry
  作者：Bargur P. Gangamani、Cheravakkattu G. Suresh、Krishna N. Ganesh

  DOI：10.1039/c39940002275

  日期：——

  X-ray crystal structures have been determined for the trans-syn photodimers 1 and 2 which are the exclusive products upon photodimerization of bis-thymines.

  反式-顺式二聚体1和2的X射线晶体结构已经确定，它们是双胸腺嘧啶光二聚化后的唯一产物。
• The rare <i>trans</i>-<i>syn</i> thymine photodimers: structures of polyoxyethylene-linked bisthymines and the derived <i>trans</i>-<i>syn</i> thymine photodimers. Comparison of the stereochemistry before and after photodimerization
  作者：C. G. Suresh、B. P. Gangamani、K. N. Ganesh

  DOI：10.1107/s0108768195012006

  日期：1996.4.1

  trans-syn Photodimer of polyoxyethylene bisthymine (1) [1,1′-(ethylenedioxydiethylene)dithymine], trans-syn-1,8-(ethylenedioxyethylene)hexahydro-4a,4b-dimethylcyclobuta[1,2-d:4,3-d′]dipyrimidine-2,4,5,7(3H,6H)-tetrone (2), C₁₆H₂₂N₄O₆, M_r = 366.4, triclinic P\bar 1}, a = 7.900 (4), b = 10.061 (8), c = 12.048 (4) Å, α = 71.37 (5), β = 78.13 (13), γ = 72.17 (5)°, V = 857.7 (9) ų, Z = 2, D_x = 1.418 g cm⁻³, μ = 0.103 mm⁻¹, F(000) = 388, R = 0.0953 for 1482 observed reflections; 1,1′-(1,2-phenylenedioxydiethylene)dithymine (3), C₂₀H₂₂N₄O₆, M_r = 414.4, triclinic, P\bar 1}, a = 8.558 (2), b = 11.077 (2), c = 11.437 (3) Å, α = 108.57 (2), β = 94.37 (2), γ = 99.77 (2)°, V = 1003.1 (4) ų, Z = 2, D_x = 1.377 g cm⁻³, μ = 0.096 mm⁻¹, F(000) = 436, R = 0.0443 for all reflections; trans-syn photodimer of (3), 1,8-(1,2-phenylenedioxydiethylene)hexahydro-4a,4b-dimethylcyclobuta[1,2-d:4,3-d′]dipyrimidine-2,4,5,7(3H,6H)-tetrone (4), C₂₀H₂₂N₄O₆, M_r = 414.4, monoclinic, P2₁/n, a = 10.357 (4), b = 14.578 (5), c = 12.676 (2) Å, β = 97.99 (3)°, V = 1895 (1) ų, Z = 4, D_x = 1.453 g cm⁻³, μ = 0.102 mm⁻¹, F(000) = 872, R = 0.0628 for 1077 observed reflections. The bisthymines (1) and (3) on photodimerization produce cyclobutane-linked trans-syn thymine dimers as the exclusive products. The planar thymines stack one above the other in (1), while they are approximately perpendicular in (3). Planarities of the thymines are altered on photodimerization. The stereochemistry around the cyclobutane ring in photoproducts (2) and (4) is highly strained. The distortions in the bond lengths and angles due to this strain are concentrated mainly on the C5 and C6 atoms, which form the interpyramidal bonds. This strain is comparatively less in the rigid catechol-linked dimer (4). The N3 atom of thymines forms hydrogen bonds in all structures. Photoproducts show closer packing compared with the parent compounds.

  反式-合成聚氧乙烯双胸腺嘧啶光二聚体 (1) [1,1′-(亚乙二氧基二乙撑基)二胸腺嘧啶]，反式-合成-1,8-(亚乙二氧基乙撑基)六氢-4a,4b-二甲基环丁并[1,2-d：4,3-d′]二嘧啶-2,4,5,7(3H,6H)-四酮 (2)，C16H22N4O6，Mr = 366.4，三菱 P\bar 1}，a = 7.900 (4)，b = 10.061 (8)，c = 12.048 (4) Å，α = 71.37 (5)，β = 78.13 (13)，γ = 72.17 (5)°，V = 857.7 (9) Å3，Z = 2，Dx = 1.418 g cm-3，μ = 0.103 mm-1，F(000) = 388，1482 个观察到的反射的 R = 0.0953；1,1′-(1,2-亚苯基二氧二乙撑)二硫杂环胺 (3)，C20H22N4O6，Mr = 414.4，三菱形，P/bar 1}，a = 8.558 (2)，b = 11.077 (2)，c = 11.437 (3) Å，α = 108.57 (2)，β = 94.37 (2)，γ = 99.77 (2)°，V = 1003.1 (4) Å3，Z = 2，Dx = 1.377 g cm-3，μ = 0.096 mm-1，F(000) = 436，R = 0.0443 for all reflections; trans-syn photodimer of (3), 1,8-(1,2-phenylenedioxydiethylene)hexahydro-4a,4b-dimethylcyclobuta[1,2-d:4,3-d′]dipyrimidine-2,4,5,7(3H,6H)-tetrone (4), C20H22N4O6, Mr. = 414.4，单斜，P21/n，a = 10.357 (4)，b = 14.578 (5)，c = 12.676 (2)埃，β = 97.99 (3)°，V = 1895 (1) Å3，Z = 4，Dx = 1.453 g cm-3，μ = 0.102 mm-1，F(000) = 872，1077 个观察到的反射的 R = 0.0628。双胸腺嘧啶（1）和（3）在光二聚化过程中产生的环丁烷连接反式-合成胸腺嘧啶二聚体是唯一的产物。在(1)中，平面的胸腺嘧啶一个叠在另一个上面，而在(3)中，它们近似垂直。胸腺嘧啶的平面度在光二聚化过程中会发生改变。光反应产物（2）和（4）中环丁烷环周围的立体化学结构高度紧张。这种应变导致的键长和键角的变形主要集中在形成斜方间键的 C5 和 C6 原子上。这种应变在刚性儿茶酚连接二聚体 (4) 中相对较小。甲状腺素的 N3 原子在所有结构中都形成氢键。与母体化合物相比，光反应产物的堆积更为紧密。