4,4'-(1,2-ethanediyl)-bis(1,7-dioxa-4,10-diazacyclododecane) | 80639-65-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4,4'-(1,2-ethanediyl)-bis(1,7-dioxa-4,10-diazacyclododecane)
• 英文别名: 1,2-ethanediylbis(1,7-dioxa-4,10-diazacyclododecane)；4,4'-(Ethane-1,2-diyl)bis(1,7-dioxa-4,10-diazacyclododecane)；4-[2-(1,7-dioxa-4,10-diazacyclododec-4-yl)ethyl]-1,7-dioxa-4,10-diazacyclododecane
• CAS: 80639-65-2
• 化学式: C₁₈H₃₈N₄O₄
• 分子量: 374.524
• InChiKey: WVTCAXOTZAPVBD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.6
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  67.5
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2,6-双(溴甲基)氟苯 、 4,4'-(1,2-ethanediyl)-bis(1,7-dioxa-4,10-diazacyclododecane) 在 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 16.0h， 以30%的产率得到34-fluoro-12,21,26,31-tetraoxa-1,9,15,18-tetrazatetracyclo[16.5.5.59,15.13,7]tetratriaconta-3(34),4,6-triene
  参考文献：
  名称：

  碳氟化合物的配位化学：氟大环化合物的第I组和第II组金属离子配合物

  摘要：

  1,3-双（溴甲基）-2-氟苯与苯并二氮杂-15-冠-5的反应合成了两个新的氟大环苯并FN 2 O 3和F（N 2 O 2）2 C 2 H 4。 1,2-双（diaza-12-crown-4）乙烷，产率分别为30％。溶液中各个碱金属络合物之间的CF ...金属离子相互作用密切，这是通过19 F-NMR共振相对于游离配体的高达δ = 18.7的特征位移和1 J（CF）的降低证明的耦合常数高达20 Hz，这在BenzoFN中最明显2 O 3 ·Li +和F（N 2 O 2）2 C 2 H 4 ·K +。在BenzoFN 2 O 3 ·Li +中，观察到15.5 Hz的1 J（ 19 F- 7 Li），这表明溶液中CF ... Li +的相互作用非常紧密。在BenzoFN 2 O 3 ·Na + [CF⃛Na + 246.8（2）pm]的X射线晶体结构中，26-氟-4,7,13,16-四恶唑-1，10-二氮杂三环[8

  DOI：

  10.1002/cber.19971300725
• 作为产物：
  描述：

  N,N-bis<2-(2-hydroxyethoxy)ethyl>-p-toluenesulfonamide 在 palladium on activated charcoal lithium aluminium tetrahydride 、 氢气 、 sodium carbonate 作用下， 以 四氢呋喃 、 吡啶 、 乙腈 为溶剂， 反应 96.0h， 生成 4,4'-(1,2-ethanediyl)-bis(1,7-dioxa-4,10-diazacyclododecane)
  参考文献：
  名称：

  阳离子络合双N，N '桥联的双-（1,7-二氧杂-4,10-二氮杂环十二烷）的合成

  摘要：

  可以在两个受控步骤中通过氮原子之间的两个乙烯桥将两个diaza-12-crown-4分子连接，其中最后一个需要以Li阳离子为模板，尽管Na阳离子与三环穴状类似物的结合最强。

  DOI：

  10.1039/c39810001084

文献信息

• Complexation of Na+ in Redox-Active Ferrocene Crown Ethers, a Structural Investigation, and an Unexpected Case of Li+ Selectivity
  作者：Herbert Plenio、Ralph Diodone

  DOI：10.1021/ic00119a018

  日期：1995.7

  The synthesis of several ferrocene crown ethers is described, which were designed tb selectively coordinate and recognize electrochemically small group I ions sandwiched between two 12-membered crown ether rings. The reactions of the [1,1'-ferrocenediylbis(methylene)]bis[pyridinium] salt [Fcdiyl(py)(2)(2+)] with diaza-12-crown-4 [H(N-2-12-C-4)H], aza-12-crown-4 [H(N-12-C-4)], and 1,2-ethanediylbis(1,7-dioxa-4,10-diazacyclododecane) [C(2)H(4)diyl-((N-2-12-C-4)H)(2)] yielded the respective ferrocene crown ethers 1,1 '':1',1'''-bis(ferrocenediyl)bis[4,10-bis(methylene)-1,7-dioxa-4,10-diazacyclododecane)] 10-diazacyclododecane)] Fcdiyl(N-2-12-C-4)(2)Fcdiyl] (3), [Fcdiyl(N-12-C-4)(2)] (2), and [Fcdiyl(N-2-12-C-4)(2)(C(2)H(4)diyl)] (4). Complexation of group 1 ions was evidenced by NMR, cyclic voltammetry, FAB mass spectrometry, and picrate extraction experiments. This last techniques was used to determine a complexation selectivity of 4 for Li+/Na+ approximate to 20:1. The redox potentials of the ligands 2, 3, and 4 were determined by cyclic voltammetry; addition of Li+ or Na+ results in anodic shifts of the redox potentials of up to 100 mV for (4Na+ and 140 mV for(4Li+. The X-ray crystal structures of [(2)NaClO4](2), [(2)NaBPh(4)](2), 3, 3 . 2HClO(4), 4, and (4)NaI were determined to understand the coordination behavior of these ligands and the metal ion selectivities displayed. The determining factor for the stability of the metal complexes is the orientation of the plane of the cyclopentadienyl (Cp) ring with respect to the CpCH(2)-N vector. In metal ion or proton complexes torsion angles of close to 90 degrees are preferred, which allow the equal participation of all donor atoms in the coordination of a cation. This property, however, prevents the complexation of Na+ or Li+ within the cavity formed by 3. Replacing one 1,1'-ferrocenediylbis(methylene) group in 3 by a sterically more suitable C2H4 bridge results in 4 and allows formation of the Na+-sandwich (4)NaI. In this complex strain is apparent, which leads to the preferential coordination of Li+ by 4. The results obtained in this study make it possible to set up a correlation of the anodic shifts Delta E of the iron redox potentials upon complexation of Na+ by ferrocene crown ethers and the inverse distance Fe-Na+ as determined by crystal structure analysis Delta E congruent to 1/(Fe-Na+). This indicates that crystal structures of metal complexes of ferrocene crown ethers can serve as reasonable models for the corresponding species in solution.
• NEW AZA-CROWN-ETHERS AND THEIR USE
  申请人：BORREGAARD INDUSTRIES LIMITED

  公开号：EP0079920B1

  公开（公告）日：1986-10-15
• Synthesis of a cation complexing doubly N,N′-bridged bis-(1,7-dioxa-4,10-diazacyclododecane)
  作者：Martin J. Calverley、Johannes Dale

  DOI：10.1039/c39810001084

  日期：——

  Two molecules of diaza-12-crown-4 can be linked by two ethylene bridges between nitrogen atoms in two controlled steps, the last of which needs Li cation as a template, although Na cation is most strongly complexed by the tricyclic cryptand-like product.

  可以在两个受控步骤中通过氮原子之间的两个乙烯桥将两个diaza-12-crown-4分子连接，其中最后一个需要以Li阳离子为模板，尽管Na阳离子与三环穴状类似物的结合最强。
• The Coordination Chemistry of Fluorocarbons: Group‐I and Group‐ II Metal Ion Complexes of Fluoro Macrocycles
  作者：Herbert Plenio、Ralph Diodone

  DOI：10.1002/cber.19971300725

  日期：1997.7

  indicative very close CF...Li+ interactions in solution. In the X-ray crystal structures of BenzoFN2O3 · Na+ [CF ⃛Na+ 246.8(2) pm], 26-fluoro-4,7,13,16-tetraoxa-1, 10-diazatricyclo[ 8.8.7.1 20,24 ] - hexacosa-20,22,24(26)triene · Na+ (CF ⃛Na+ 267.1(2) pm) and 21 -fluoro-3,6,9,12,15,18-hexaoxabicyclo[ 18.3.1 1,20]heneicosa- l(24),20,22-triene. Ba2+ [CF ⃛Ba2+ 299.0(3) pm] short CF ⃛metal interactions were

  1,3-双（溴甲基）-2-氟苯与苯并二氮杂-15-冠-5的反应合成了两个新的氟大环苯并FN 2 O 3和F（N 2 O 2）2 C 2 H 4。 1,2-双（diaza-12-crown-4）乙烷，产率分别为30％。溶液中各个碱金属络合物之间的CF ...金属离子相互作用密切，这是通过19 F-NMR共振相对于游离配体的高达δ = 18.7的特征位移和1 J（CF）的降低证明的耦合常数高达20 Hz，这在BenzoFN中最明显2 O 3 ·Li +和F（N 2 O 2）2 C 2 H 4 ·K +。在BenzoFN 2 O 3 ·Li +中，观察到15.5 Hz的1 J（ 19 F- 7 Li），这表明溶液中CF ... Li +的相互作用非常紧密。在BenzoFN 2 O 3 ·Na + [CF⃛Na + 246.8（2）pm]的X射线晶体结构中，26-氟-4,7,13,16-四恶唑-1，10-二氮杂三环[8