5,11,17,23-Tetra-tert-butyl-25,27-bis(allyloxy)-26,28-dimethoxycalix[4]arene | 163836-75-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5,11,17,23-Tetra-tert-butyl-25,27-bis(allyloxy)-26,28-dimethoxycalix[4]arene
• 英文别名: 5,11,17,23-Tetratert-butyl-25,27-dimethoxy-26,28-bis(prop-2-enoxy)pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaene
• CAS: 163836-75-7
• 化学式: C₅₂H₆₈O₄
• 分子量: 757.11
• InChiKey: PKJQBZOMEHHVSR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.5
• 重原子数：
  56
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5,11,17,23-Tetra-tert-butyl-25,27-bis(allyloxy)-26,28-dimethoxycalix[4]arene 在 sodium hydroxide 、 硼烷四氢呋喃络合物 、 双氧水 作用下， 生成 5,11,17,23-Tetra-tert-butyl-25,27-bis(3-hydroxypropoxy)-26,28-dimethoxycalix<4>arene
  参考文献：
  名称：

  Synthesis and Structural Characterization of Calix[4]arenes, Calix[6]arenes, and Calix[8]arenes with 3-Hydroxypropoxy or 2-Hydroxyethoxy Functional Groups Appended onto the Lower Rim

  摘要：

  The compound 5,11,17,23,29,35-hexa-tert-butyl-37,39,41-trihydroxy-38,40,42-trimethoxycalix[6]arene, 1, has been prepared by treating 5,11,17,23,29,35-hexa-tert-butylcalix[6]arene with potassium carbonate, followed by methyl p-toluenesulfonate. The analogous reaction with the unsubstituted calix[6]arene gives 37,38,39-trihydroxy-40,41,42-trimethoxycalix[6]arene 2. Treating 1 or 5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26,28-dimethoxycalix[4]arene 3, with sodium hydride followed by allyl bromide gives 5,11,17,23,29,35-hexa-tert-butyl-37,39,41-tris(allyloxy)-38,40,42-trimethoxycalix[6]arene, 4, or 5,11,17,23-tetra-tert-butyl-25,27-bis(allyloxy)-26,28-dimethoxycalix[4]arene, 5, respectively. Compounds 4 and 5 react with BH3, followed by H2O2 to give 5,11,17,23,29,35-hexa-tert-butyl-37,39,41-tris(3-hydroxypropoxy)-38,40,42-trimethoxycalix[6] arene, 6, and 5,11,17,23-tetra-tert-butyl-25,27-bis(3-hydroxypropoxy)-26,28-dimethoxycalix[4]arene, 7, respectively. A general procedure for the synthesis of 2-hydroxyethoxy-substituted calixarenes involves reduction of the corresponding ethyl calixaryl acetates with LiAlH4. The procedure has been used to synthesize 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(2-hydroxyethoxy)calixarene, 8, 25,26,27,28-tetra(2-hydroxyethoxy)calix[4]arene, 9, 5,11,17,23,29,35-hexa-tert-butyl-37,38,39,40,4142-hexakis(2-hydroxyethoxy)calix[6]arene 10, 37,38,39,40,41,42-hexa(2-hydroxyethoxy)calix[6]arene, 11, 5,11,17,23,29,35,41,47-octa-tert-butyl-49,50,51,52,53,54,55,56-octakis(2-hydroxyethoxy)calix[8]arene, 12, and 49,50,51,52,53,54,55,56-octakis(2-hydroxyethoxy)calix[8]arene, 13. Compounds 2, 4, 5, 9, and 10 have been characterized by X-ray crystallography. The conformations of the tetrols, hexols, and octols have been computationally explored using molecular mechanics calculations.

  DOI：

  10.1021/jo00099a032
• 作为产物：
  描述：

  1,3-二甲氧基-4-叔丁基杯芳烃 、 3-溴丙烯 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 以69%的产率得到5,11,17,23-Tetra-tert-butyl-25,27-bis(allyloxy)-26,28-dimethoxycalix[4]arene
  参考文献：
  名称：

  杯[4]芳烃混合四醚的构象控制。第2部分

  摘要：

  通过两个制备了一系列杯[4]亚芳基和对叔丁基杯[4]亚芳基的混合四醚，其中两个末端取代基是甲基，另外两个具有3、4和5个碳原子链的1-烯基在引入基团（甲基或烯基）的顺序上不同的途径。对-叔丁基杯[4]芳烃的醚在动态平衡状态下以圆锥（次要）和部分圆锥（主要）构象的混合物形式分离出来。对于杯[4]芳烃的醚，其构象结果取决于合成方法。最多可以检测到三个构象：一个圆锥体，一个带有茴香基单元的部分圆锥体以及一个带有烯基轴承环的部分圆锥体。1个对这些醚与碱金属碘化物之间形成的络合物的1 H NMR分析表明，碘化锂可检测到对叔丁基杯[4]芳烃四醚的圆锥和部分圆锥络合物，但只有杯形的圆锥络合物[4]。 ]芳烃衍生物。两组化合物也都形成了碘化钠配合物，但在所有情况下都只检测到了锥体配合物。

  DOI：

  10.1016/s0040-4020(97)10078-3

文献信息

• Conformational control in the synthesis of mixed tetraethers of calix[4]arene. Part 2
  作者：Miguel Pitarch、Julie K. Browne、M.Anthony McKervey

  DOI：10.1016/s0040-4020(97)10078-3

  日期：1997.11

  A series of mixed tetraethers of calix[4]arene and p-tert-butylcalix[4]arene in which two distal substituents are methyl and the other two 1-alkenyl groups with 3, 4 and 5 carbon atom chains have been prepared by two routes which differ in the order in which the groups (methyl or alkenyl) were introduced. The ethers of p-tert-butylcalix[4]arene were isolated as a mixture of cone (minor) and partial

  通过两个制备了一系列杯[4]亚芳基和对叔丁基杯[4]亚芳基的混合四醚，其中两个末端取代基是甲基，另外两个具有3、4和5个碳原子链的1-烯基在引入基团（甲基或烯基）的顺序上不同的途径。对-叔丁基杯[4]芳烃的醚在动态平衡状态下以圆锥（次要）和部分圆锥（主要）构象的混合物形式分离出来。对于杯[4]芳烃的醚，其构象结果取决于合成方法。最多可以检测到三个构象：一个圆锥体，一个带有茴香基单元的部分圆锥体以及一个带有烯基轴承环的部分圆锥体。1个对这些醚与碱金属碘化物之间形成的络合物的1 H NMR分析表明，碘化锂可检测到对叔丁基杯[4]芳烃四醚的圆锥和部分圆锥络合物，但只有杯形的圆锥络合物[4]。 ]芳烃衍生物。两组化合物也都形成了碘化钠配合物，但在所有情况下都只检测到了锥体配合物。
• Moran Justin K., Georgiev Emil M., Yordanov Alex T., Mague Joel T., Round+, J. Org. Chem, 59 (1994) N 20, S 5990-5998
  作者：Moran Justin K., Georgiev Emil M., Yordanov Alex T., Mague Joel T., Round+

  DOI：——

  日期：——
• Synthesis and Structural Characterization of Calix[4]arenes, Calix[6]arenes, and Calix[8]arenes with 3-Hydroxypropoxy or 2-Hydroxyethoxy Functional Groups Appended onto the Lower Rim
  作者：Justin K. Moran、Emil M. Georgiev、Alex T. Yordanov、Joel T. Mague、D. Max Roundhill

  DOI：10.1021/jo00099a032

  日期：1994.10

  The compound 5,11,17,23,29,35-hexa-tert-butyl-37,39,41-trihydroxy-38,40,42-trimethoxycalix[6]arene, 1, has been prepared by treating 5,11,17,23,29,35-hexa-tert-butylcalix[6]arene with potassium carbonate, followed by methyl p-toluenesulfonate. The analogous reaction with the unsubstituted calix[6]arene gives 37,38,39-trihydroxy-40,41,42-trimethoxycalix[6]arene 2. Treating 1 or 5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26,28-dimethoxycalix[4]arene 3, with sodium hydride followed by allyl bromide gives 5,11,17,23,29,35-hexa-tert-butyl-37,39,41-tris(allyloxy)-38,40,42-trimethoxycalix[6]arene, 4, or 5,11,17,23-tetra-tert-butyl-25,27-bis(allyloxy)-26,28-dimethoxycalix[4]arene, 5, respectively. Compounds 4 and 5 react with BH3, followed by H2O2 to give 5,11,17,23,29,35-hexa-tert-butyl-37,39,41-tris(3-hydroxypropoxy)-38,40,42-trimethoxycalix[6] arene, 6, and 5,11,17,23-tetra-tert-butyl-25,27-bis(3-hydroxypropoxy)-26,28-dimethoxycalix[4]arene, 7, respectively. A general procedure for the synthesis of 2-hydroxyethoxy-substituted calixarenes involves reduction of the corresponding ethyl calixaryl acetates with LiAlH4. The procedure has been used to synthesize 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(2-hydroxyethoxy)calixarene, 8, 25,26,27,28-tetra(2-hydroxyethoxy)calix[4]arene, 9, 5,11,17,23,29,35-hexa-tert-butyl-37,38,39,40,4142-hexakis(2-hydroxyethoxy)calix[6]arene 10, 37,38,39,40,41,42-hexa(2-hydroxyethoxy)calix[6]arene, 11, 5,11,17,23,29,35,41,47-octa-tert-butyl-49,50,51,52,53,54,55,56-octakis(2-hydroxyethoxy)calix[8]arene, 12, and 49,50,51,52,53,54,55,56-octakis(2-hydroxyethoxy)calix[8]arene, 13. Compounds 2, 4, 5, 9, and 10 have been characterized by X-ray crystallography. The conformations of the tetrols, hexols, and octols have been computationally explored using molecular mechanics calculations.
• 'Soft' Calixarenes&amp;ndash;Structural Aspects of Calixarene Allyl Ethers and of Thiacalixarene Synthesis
  作者：Xavier Delaigue、Jack M. Harrowfield、M. Wais Hosseini、Mauro Mocerino、Brian W. Skelton、Allan H. White

  DOI：10.1071/c97095

  日期：——

  Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for an array of p-t-butylcalix[n]arenes, n = 4 or 6, diversely functionalized at the phenolic oxygen atoms: the 1,3-diallyl 2,4-dimethyl ether for n = 4 (1), the hexaallyl ether for n = 6 (2), and the 1,3-dibenzyl 2,4-bis(dimethylthiocarbamoyl) derivative for n = 4 (3), with a view to establishing ligand baseline conformations for subsequent metal complexation studies, and for exploring any inclusion properties. Compound (1) is monoclinic, P21/c, a 16·751(9), b 20·772(7), c 27·91(1) Å, β 99·39(4)°, Z = 8, conventional R on |F| being 0·060 for No 4396 'observed' (I > 3σ(I )) reflections. Compound (2) is triclinic, P-1, a 19·63(2), b 14·57(2), c 14·188(9) Å, α 107·84(8), β 93·26(7), γ 99·48(10)°, Z = 2, R 0·067 for No 7315. Compound (3), as its methanol monosolvate, is triclinic, P-1, a 15·592(4), b 15·17(3), c 14·31(2) Å, α 88·8(1), β 64·3(1), γ 75·7(1)°, Z = 2, R 0·076 for No 3802. The conformation of (1) is similar to that previously established for an analogue in which two of the t-butyl groups were absent; the conformation of (2) is that of a flattened 1,2,3-alternate form, the asymmetric unit being a pair of half (centrosymmetric) dimers; the conformation of (3) is 1,3-alternate.

  合成和室温单晶 X 射线结构测定 记录了一系列 对叔丁基钙[n]烯、 n = 4 或 6，在酚氧原子上具有多种官能团 酚氧原子官能化的 1,3-二烯丙基 2,4-二甲基醚为 n = 4 (1)，六烯丙基醚 n = 6 的六烯丙基醚 (2)，以及 1,3-二苄基 2,4-双（二甲基硫代氨基甲酰）衍生物（n = 4）(3)。 4 的 1,3-二苄基 2,4-双（二甲基硫代硫代氨基甲酰）衍生物 (3)，以期为随后的金属络合研究 的 1,3-二苄基 2,4-双（二甲基硫代氨基甲酰基）衍生物 (3)，以建立配体的基线构象，用于后续的金属配位研究，并探索其是否具有任何 特性。化合物 (1) 呈单斜型、 P21/c、 a 16-751（9），b 20-772(7), c 27-91(1) Å, β 99-39(4)°，Z = 8，常规 F|上的 R 为 0-060，No 4396 观测到的"（I >； 3σ(I )) 反射。化合物 (2) 为三棱体、 P-1，a 19-63(2), b 14-57(2), c 14-188(9) Å, α 107-84(8)、 β 93-26(7)，γ 99-48(10)°，Z = 2, R 0-067 for No 7315。化合物 (3) 的 化合物 (3) 的甲醇单溶物为三棱体、 P-1，a 15-592(4), b 15-17(3), c 14-31(2) Å, α 88-8(1), β 64-3(1), γ 75-7(1)°, Z = 2、 R 0-076 为 编号 3802。(1) 的构象 的构象与之前为一个类似物确定的构象相似，该类似物中的两个 (2)的构象是扁平的 1,2,3-互变异构体。 1,2,3-互变形式，其不对称单元是一对半（中心对称）二聚体。 (中心对称）二聚体；(3) 的构象为 1,3-互变形式。