15,17-dimethyl-16,18-dimethoxy-3,6,9,12-tetraoxabicyclo<12.3.1>octadeca(1,14,16)triene | 120108-74-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 15,17-dimethyl-16,18-dimethoxy-3,6,9,12-tetraoxabicyclo<12.3.1>octadeca(1,14,16)triene
• 英文别名: (2,5-dimethoxy-4,6-dimethyl-1,3-xylylene)-15 crown-4；16,18-Dimethoxy-15,17-dimethyl-3,6,9,12-tetraoxabicyclo[12.3.1]octadeca-1(17),14(18),15-triene
• CAS: 120108-74-9
• 化学式: C₁₈H₂₈O₆
• 分子量: 340.417
• InChiKey: KRYJJTNRBVZWPE-UHFFFAOYSA-N

物化性质

• 沸点：
  521.1±50.0 °C(Predicted)
• 密度：
  1.054±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  15,17-dimethyl-16,18-dimethoxy-3,6,9,12-tetraoxabicyclo<12.3.1>octadeca(1,14,16)triene 在 ammonium cerium(IV) nitrate 作用下， 以 水 、 乙腈 为溶剂， 反应 0.75h， 以79%的产率得到15,17-dimethyl-3,6,9,12-tetraoxabicyclo[12.3.1]octadeca-1(17),14-diene-16,18-dione
  参考文献：
  名称：

  Synthesis of 1,4-Benzoquinone Derivatives Having Two Side-Armed Polyethers and Crown Ethers, and Their Electrochemical Study in the Presence of Alkali Metal Cations (Na⁺and K⁺)

  摘要：

  制备出了几种具有可还原醌基的冠醚和两种侧臂聚醚。其中一些（7a、7b 和 7d）在电化学还原时对 Na+ 阳离子显示出高度增强的阳离子结合特性。

  DOI：

  10.1246/bcsj.61.3026
• 作为产物：
  描述：

  3,5-二甲基-4-氨基苯酚 在 盐酸 、 sodium hydroxide 、 sodium dithionite 、 三氯化铁 作用下， 以 四氢呋喃 、 水 为溶剂， 生成 15,17-dimethyl-16,18-dimethoxy-3,6,9,12-tetraoxabicyclo<12.3.1>octadeca(1,14,16)triene
  参考文献：
  名称：

  Synthesis of 1,4-Benzoquinone Derivatives Having Two Side-Armed Polyethers and Crown Ethers, and Their Electrochemical Study in the Presence of Alkali Metal Cations (Na⁺and K⁺)

  摘要：

  制备出了几种具有可还原醌基的冠醚和两种侧臂聚醚。其中一些（7a、7b 和 7d）在电化学还原时对 Na+ 阳离子显示出高度增强的阳离子结合特性。

  DOI：

  10.1246/bcsj.61.3026

文献信息

• Unusual Me−O Bond Cleavage in a Metalated Crown-Ether:  X-ray Molecular Structure of (5-Methoxy-4,6-dimethyl-1,3-xylylene-2-one)-15 Crown-4 Complex of Pentamethylcyclopentadienyl Iridium
  作者：H. Amouri、J. Vaissermann、M. N. Rager、Y. Besace

  DOI：10.1021/ic980811s

  日期：1999.3.1

  reaction of [(C(5)Me(5))Ir(Solvent)(3)][BF(4)](2) (1) with (2,5-dimethoxy-4,6-dimethyl-1,3-xylylene)-15 crown-4 (2) affords the metalated crown-ether complex [(eta(5)-C(5)Me(5))Ir(eta(6)-C(18)H(28)O(6))][BF(4)](2) (3) in 88% yield. Complex 3 undergoes a facile Me-O bond cleavage to give the related semiquinone form of the metalated crown-ether [(eta(5)-C(5)Me(5))Ir(eta(5)-C(17)H(25)O(6))][BF(4)] (4)

  [[C（5）Me（5））Ir（溶剂）（3）] [BF（4）]（2）（1）与（2,5-二甲氧基-4,6-二甲基-1， 3-二甲苯基）-15 Crown-4（2）提供金属化的冠醚复合物[（eta（5）-C（5）Me（5））Ir（eta（6）-C（18）H（28） O（6））] [BF（4）]（2）（3），产率为88％。配合物3进行容易的Me-O键裂解以产生相关的半醌形式的金属化冠醚[（eta（5）-C（5）Me（5））Ir（eta（5）-C（17）H （25）O（6））] [BF（4）]（4）。报告了配合物4的单晶X射线结构测定。配合物4在单斜空间群P2（1）/ m中结晶，其中a = 8.187（5）Å，b = 17.193（4）Å，c = 10.900（3）Å，alpha = 90度，beta = 109.68（1 ）度，伽玛= 90度，Z =2。该结构为我们提供了有关金属化冠醚的eta（5
• Redox-active crown ethers. Electrochemical and electron paramagnetic resonance studies on alkali metal complexes of quinone crown ethers
  作者：Milagros Delgado、Robert E. Wolf、JudithAnn R. Hartman、Gillian McCafferty、Rahmi Yagbasan、Simon C. Rawle、David J. Watkin、Stephen R. Cooper

  DOI：10.1021/ja00049a032

  日期：1992.11

  Structural studies on [M(NCS).(5QC-HQDME)] (M = Li, Na) as well as free 6QC-HQDME and [M(NCS). (6QC-HQDME)] (M = Na, K) (where 5QC-HQDME is 15,17-dimethyl-16,18-dimethoxy-3,6,9,12-tetraoxabicyclo[12.3.1]octadeca(1,14,16)triene, and 6QC-HQDME is 15,17-dimethyl-16,18-dimethoxy-3,6,9,12,15-pentaoxabicyclo[15.3.1]heneico(1,14,16)triene) show that in all cases the metal ion binds to the anisole oxygen atom in the 1-position. Only in the case of [K(NCS).(6QC-HQDME)] do both benzylic O atoms bind to the metal ion; in the other complexes only one of these O atoms interacts with M+. In each complex all of the non-benzylic crown O atoms coordinate. These results indicate that the benzylic O atoms contribute suboptimally to complexation. Crystallographic data are as follows: [Li(NCS). (5QC-HQDME)], monoclinic, C19H28NO6SLi, space group P2(1)/n, a = 14.103 (4) angstrom, b = 8.493 (4) angstrom, c = 19.128 (8) angstrom, beta = 108.70 (9)-degrees, Z = 4; [Na(NCS).(5QC-HQDME)], monoclinic, C19H28NO6SNa, space group P2(1)/c, a = 10.182 (4) angstrom, b = 8.601 (1) angstrom, c = 25.631 (3) angstrom, beta = 97.29 (3)-degrees, Z = 4; 6QC-HQDME, orthohombic, C20H32O7, space group P2(1)2(1)2(1), a = 8.195 (1) angstrom, b = 11.541 (1) angstrom, c = 22.449 (3) angstrom, Z = 4; [Na(NCS).(6QC-HQDME)].MeCN, monoclinic, C23H35N2O7SNa, space group P2(1)/c, a = 11.308 (1) angstrom, b = 14.521 (2) angstrom, c = 16.440 (4) angstrom, beta = 91.56 (1)-degrees, Z = 4; [K(NCS).(6QC-HQDME)], monoclinic, C21H32NO7SK, space group P2(1)/c, a = 17.377 (3) angstrom, b = 10.600 (2) angstrom, c = 27.538 (7) angstrom, beta = 102.41 (3)-degrees, Z = 8. Electrochemical and EPR studies show that redox-active crown ethers incorporating quinone groups successfully couple ion binding by the crown ether to the redox state of the quinone group. Alkali metal ions cause potential shifts that establish-differential redox-induced complexation that qualitatively and quantitatively differs from ion-pairing effects. They also perturb the EPR hyperfine splittings in the semiquinone moieties in a characteristic fashion, as well as in one case giving rise to Na-23 superhyperfine splitting.
• TOGO, HIDEO;HASHIMOTO, KIICHI;MORIHASHI, KENJI;KIKUCHI, OSAMU, BULL. CHEM. SOC. JAP., 61,(1988) N 8, C. 3026-3028
  作者：TOGO, HIDEO、HASHIMOTO, KIICHI、MORIHASHI, KENJI、KIKUCHI, OSAMU

  DOI：——

  日期：——
• Synthesis of 1,4-Benzoquinone Derivatives Having Two Side-Armed Polyethers and Crown Ethers, and Their Electrochemical Study in the Presence of Alkali Metal Cations (Na⁺and K⁺)
  作者：Hideo Togo、Kiichi Hashimoto、Kenji Morihashi、Osamu Kikuchi

  DOI：10.1246/bcsj.61.3026

  日期：1988.8

  Several crown ethers and two side-armed polyethers which have reducible quinonoid groups were prepared. Some of them, 7a, 7b, and 7d, showed highly enhanced cation-binding properties for the Na+ cation upon electrochemical reduction.

  制备出了几种具有可还原醌基的冠醚和两种侧臂聚醚。其中一些（7a、7b 和 7d）在电化学还原时对 Na+ 阳离子显示出高度增强的阳离子结合特性。