1,5,9,13-tetraselenacyclohexadecan-3,11-diol | 177854-84-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,5,9,13-tetraselenacyclohexadecan-3,11-diol
• 英文别名: 1,5,9,13-Tetraselenacyclohexadecane-3,11-diol
• CAS: 177854-84-1
• 化学式: C₁₂H₂₄O₂Se₄
• 分子量: 516.161
• InChiKey: RGXYFWSZEYJAFF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.67
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  copper(II) bis(trifluoromethanesulfonate) 、 1,5,9,13-tetraselenacyclohexadecan-3,11-diol 以 硝基甲烷 、 二氯甲烷 为溶剂， 以49%的产率得到(1,5,9,13-tetraselenacyclohexadecan-3,11-diol)copper(II)trifluoromethanesulfonate
  参考文献：
  名称：

  新硒化钴和硒化铜（I）和铜（II）配合物的合成，表征和氧化还原行为。

  摘要：

  The synthesis and characterization of new selenium coronands and of copper(I) and copper(II) complexes of selenium coronands are reported. Molecular structures in the solid state have been determined by X-ray crystallography. The molecular structures of 6,7,13,14-dibenzo-1,5,8,12-tetraselenacy (dibenzo-14Se4 (1)) and 1,5,9-triselenacyclododecane (12Se3 (2)) adopt conformations which maximize the number of possible gauche C-Se-C-C bond torsion angles. 1: T = 190 K; orthorhombic, space group Pca2(1); fw = 552.19; Z = 4; a = 9.645(3) Angstrom; b = 12.679(6) Angstrom; c 15.332(4) Angstrom; V = 1874.9 Angstrom(3); R-F = 0.027 for 1732 data (I-o greater than or equal to 2.5 sigma(I-o)) and 200 variables. 2: T = 190 K; orthorhombic, space group Pn2(1)a; fw = 363.12; Z = 4; a = 14.943(4) Angstrom, b = 5.638(2) Angstrom; c = 14.229(3) Angstrom, V = 1198.8 Angstrom(3); R-F = 4.026 for 862 data (I-o greater than or equal to 2.5 sigma(I-o)) and 111 variables. The molecular structures of 1,5-diselena-9,13-dithiacyclohexadecane (16Se2S2 (3)) and [Cu(16Se2S2)][SO3CF3](2) (4) correspond to those displayed by both of the analogous tetrathia and tetraselena macrocycles. Compound 3 adopts a [3535] quadrangular conformation. Compound 4, [Cu(16Se4(OH)2][SO3CF3](2) (5) (where 16Se4(OH)(2) = cis-1,5,9,13-tetraselenacyclohexadecane-3,11-diol), and [Cu(8Se2(OH))(2)][SO3CF3](2) (6) (where 8Se2(OH) = 1.5-diselenacyclooctan-3-ol) have typical tetragonally distorted octahedral coordination environments of Cu(II). Compounds 4 and 5 both display a c,t,c configuration of the coronand. Compound 5 has only one hydroxyl group coordinated in an axial position, which requires that the corresponding Se-Cu-Se-C-C-C ring be locked into a boat rather than a chair conformation.The hydroxyl groups in 6 occupy the axial coordination positions. 3: T = 200 K; monoclinic, space group C2/c; fw = 390.36; Z = 12; a = 24.202(9) Angstrom; b = 18.005(7) Angstrom; c 16.235(5) Angstrom; beta 138.23(3)degrees; V = 4713 Angstrom(3); R-F = 0.052 for 1881 data (I-o greater than or equal to 2.5 sigma(I-o)) and 172 variables. 4: T = 297 K: monoclinic, space group P2(1)/n; fw = 752.03; Z = 2; a = 8.882(2) Angstrom; b = 10.874(2) A; c = 13.360(2) Angstrom; beta = 97.95(2)degrees; V = 1277.9 Angstrom(3); R-F = 0.028 for 1610 data (I-o greater than or equal to 2.5 sigma(I-o)) and 176 variables. 5: T = 190 K; monoclinic, space group P2(1)/n; fw = 877.84; Z = 4; a = 8.412(5) Angstrom; b = 20.924(5) Angstrom; c = 15.021(5) Angstrom; beta = 100.82(4)degrees; V = 2597 Angstrom(3); R-F = 0.059 for 2152 data (I-o greater than or equal to 2.5 sigma(I-o)) and 185 variables. 6: T = 195 K; monoclinic, space group P2(1)/c; fw = 877.84; Z = 2; a = 6.675(2) Angstrom; b = 10.945(2) Angstrom; c = 17.496(2) Angstrom, beta = 96.76(2)degrees; V = 1307.3 Angstrom(3); R-F = 0.023 for 1816 data (I-o greater than or equal to 2.5 sigma(I-o)) and 159 variables. [Cu(16Se2S2)][SO3CF3] (7) and [Cu(16Se4(OH))][SO3CF3] (8) (where 16Se4(OH) = 1,5,9,13-tetraselenacyclohexadecan-3-ol) are both terrahedral Cu(I) coronand complexes with typical t,t,t configurations.7. T = 205 K; triclinic, space group P (1) over bar; fw = 602.97; Z = 2; a = 10.512(3) Angstrom; b = 10.674(2) Angstrom; c = 10.682(3) Angstrom; alpha = 101.47(2)degrees; beta = 116.82(2)degrees; gamma = 93.59(2)degrees; V = 1032.3 Angstrom(3); R-F = 0.029 for 2237 data (I-o greater than or equal to 2.5 sigma(I-o)) and 264 variables. 8: T = 297 K; monoclinic, space group P2(1)/n; fw = 712.77; Z = 4; a = 13.695(2) Angstrom; b = 11.202(2) Angstrom; c = 14.163(3) Angstrom; beta = 92.35(2)degrees; V = 2170.9 Angstrom(3); R-F = 0.035 for 2086 data (I-o greater than or equal to 2.5 sigma(I-o)) and 189 variables. Compounds 5, 6, and 8 all display hydrogen bonding between hydroxyl groups and the SO3CF3- ions. Isotropic C-13 and Se-77 chemical shifts have been obtained in the solid state for 2,3,1,5,9,13-tetraselenacyclohexadecane-3, 11-diol (16Se4(OH)(2) (9)), 1,5,9,13-etraselenacyclohexadecan-3-ol (16Se4(OH) (10)), and the dicationic complex 1,5,-(diseleniacyclooctane trifluoromethanesulfonate (8Se2(SO3CF3)(2) (11)). In addition, the Se-77 chemical shift anisotropies have been determined for 10 and 11. The dicationic compound 11 resonates at lower field, reflective of a contribution from the transannular Se-Se bond. The redox behavior of 1-8 has been examined by means of cyclic voltammetry. Redox behavior of the copper complexes 4, 5, and 6 indicates the presence of two different conformational isomers of the Cu(I) complexes that are oxidized at different potentials, analogous to Rorabacher's copper(II/I) complexes that follow a dual-pathway square-scheme mechanism. The quasi-reversible cyclic voltammograms observed for the Cu(II) complexes of selenium coronands reflect the configurational changes between Cu(II) complexes (octahedral or tetragonal configurations) and Cu(T) complexes (tetrahedral configurations) and indicate that the configurational changes are slower than the electron transfers to the electrode.

  DOI：

  10.1021/ic991345p
• 作为产物：
  描述：

  1,3-二溴丙烷 、 1,3-Bis-selenocyanato-propan-2-ol 在 sodium tetrahydroborate 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 20.0h， 以11%的产率得到1,5,9,13-tetraselenacyclohexadecan-3,11-diol
  参考文献：
  名称：

  Synthesis and characterization of polymer-bound selenium coronands: enhancing the stability of reactive dications by restricting intermolecular interactions

  摘要：

  描述了从钠丙烷-1,3-双硒酰醇酸盐-2-醇与4,8-二硒基十一烷-1,11-二对甲苯磺酸盐5在THF和乙醇中反应，得到1,5,9,13-四硒杂环十六烷-3-醇7的逐步合成，收率为62%。化合物5是从相应的二醇3获得的，而二醇3则是从钠丙烷-1,3-双硒酰醇酸盐与两当量的3-氯丙醇反应而得。1,5-二硒杂环辛烷-3-醇9和1,5,9,13-四硒杂环十六烷-3,11-二醇10分别从钠丙烷-1,3-双硒酰醇酸盐-2-醇与1,3-二溴丙烷的一步反应中得到，收率分别为43%和11%。通过自由基聚合法制备了具有挂链硒冠状体的聚合物，即1,5-二硒杂环辛烷（8Se2）和1,5,9,13-四硒杂环十六烷（16Se4），它们是由相应的硒冠状体9和7经过衍生化为丙烯酰酯11和12而制备的。类似地，还制备了甲基丙烯酸甲酯和3,7-二硒杂环辛基丙烯酸酯11的共聚物。通过核磁共振、红外和紫外-可见光谱对聚合物进行了表征。通过电化学方法确定了溶液中和电极上涂覆的薄膜形式的聚合物结合的硒冠状体的氧化还原化学。与单体类似物相比，连接到聚合物链上的硒冠状体表现出更强的氧化稳定性，可能是因为聚合物结合的官能团的受限运动抑制了分子内和分子间的降解反应。聚合物修饰电极的电活性仅限于靠近电极表面的几层分子。通过与电化学惰性的甲基丙烯酸甲酯共聚合，实现了冠状体沿链的空间分离，从而获得了比相应的同聚物更大的氧化还原稳定性的共聚物修饰电极。此外，通过将电化学惰性的聚甲基丙烯酸甲酯与电活性的硒冠状体共聚合，获得了具有更优异的电化学稳定性的聚合物修饰电极。关键词：硒冠状体、聚合物、电化学、二阳离子。

  DOI：

  10.1139/v96-058