5,11,17,23-tetracyanomethyl-25,26,27,28-tetra(benzyloxy)calix[4]arene | 152499-18-8

• 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-tetracyanomethyl-25,26,27,28-tetra(benzyloxy)calix[4]arene
• 英文别名: 2-[11,17,23-Tris(cyanomethyl)-25,26,27,28-tetrakis(phenylmethoxy)-5-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-dodecaenyl]acetonitrile
• CAS: 152499-18-8；157749-12-7
• 化学式: C₆₄H₅₂N₄O₄
• 分子量: 941.141
• InChiKey: PXEVIAFGQKRUQQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.2
• 重原子数：
  72
• 可旋转键数：
  16
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  132
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  5,11,17,23-tetracyanomethyl-25,26,27,28-tetra(benzyloxy)calix[4]arene 在 三氯化铝 、 sodium hydride 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 8.5h， 生成 5,11,17,23-Tetrakis<1-cyano-2-(2'-thienyl)ethenyl>-25,26,27,28-tetrahydroxycalix<4>arene
  参考文献：
  名称：

  Calixarenes. 40. Arylmethylenation of p-(Cyanomethyl)calix[4]arene

  摘要：

  Treatment of tetra-O-substituted p-(cyanomethyl)calix[4]arenes 3 and 6 with aromatic aldehydes yields aldol product resulting from condensation at the carbons a to the cyano groups. The products 4 from the tetra-O-benzyl compound 3 retain the benzyl groups and are formed in the 1,3-alternate conformation. The products 7 from the tetra-O-benzoyl compounds 6, however, involve loss of the benzoyl groups and are formed in the cone conformation. The same phenolic compounds 7 can be obtained from the O-benzyl compounds 4 by Lewis acid-induced removal of the benzyl groups. Reintroduction of the benzyl groups by treating 7 with benzyl bromide produces the tetra-O-benzylated product in the cone conformation (12) when NaH is used as the base or in the 1,3-alternate conformation (4) when K2CO3 is used as the base. Benzoylation of 7 produces the tetra-O-benzoyl compound in the 1,3-alternate conformation (10) when 1-methylimidazole is used as the base or the 1,3-di-O-benzoyl compound in a flattened cone conformation (11) when AlCl3 is used as the catalyst. H-1 NMR and C-13 NMR data provide support for the conformational assignments, and UV data suggest a twisting of the conjugated system in the 2'-substituted compounds 4b/7b (2'-methoxyphenyl), 4e/7e (2'-methylphenyl), and 4g/7g (2'-chlorophenyl).

  DOI：

  10.1021/jo00099a038
• 作为产物：
  描述：

  p-cyanomethylcalix[4]arene 、 alkaline earth salt of/the/ methylsulfuric acid 在 potassium carbonate 、 sodium iodide 作用下， 以 丙酮 为溶剂， 以91%的产率得到5,11,17,23-tetracyanomethyl-25,26,27,28-tetra(benzyloxy)calix[4]arene
  参考文献：
  名称：

  Selective Arylmethylation, Arylmethenylation and Aroylation of Mono- and Tetra-p-Cyanomethylcalix[4]arene

  摘要：

  四氰甲基钙克[4]芳烃（3）在不同量的碳酸钾存在下，与苄基卤化物反应，选择性地转化为其四苄醚4（1,3-alternate构象）和1,3-二苄醚5（锥构象）。单氰甲基钙克[4]芳烃（6）仅生成1,3-二取代产物7的锥构象（苄基部分连接到未取代的环）。在氢化钠存在下对6进行芳酰化反应生成四取代产物9，而与氯化铝反应则产生易于分离的1,3-二取代化合物10和11的混合物。令人惊讶的是，使用1-甲基咪唑作为碱时未能实现区域选择性。另一方面，6与4-溴苯磺酰氯在相同反应条件下反应，生成四取代产物12的锥构象。使用氢化钠作为碱，6与苄基卤化物或苯甲醛反应，分别生成完全苄基化合物8或苄基衍生物13。

  DOI：

  10.1055/s-1995-4075

文献信息

• Heavily-substituted calix[4]arenes derived from p-Cyanomethylcalix[4]arene
  作者：Shiv Kumar Sharma、C.David Gutsche

  DOI：10.1016/s0040-4020(01)86706-5

  日期：1994.4

  p-Cyanomethylcalix[4]arene (1b) can be converted in good yield to compounds containing twelve arylmethyl groups, four attached to the phenolic oxygens and eight to the carbons α to the CN groups. Depending upon the reaction protocol the products can be obtained either in the 1,3-alternate (3) or cone (4) conformation. Complete debenzylation or selective debenzylation (to monohydroxy and trihydroxy

  对氰基甲基杯[4]芳烃（1b）可以高收率转化为含有十二个芳基甲基，四个与酚氧相连的碳原子和八个与CN基碳原子相连的碳原子的化合物。取决于反应方案，可以以1，3-交替（3）或圆锥（4）构型获得产物。可以分别用AlCl 3和Me 3 SiBr进行完全脱苄基作用或选择性脱苄基作用（生成单羟基和三羟基化合物）。
• Upper Rim Substitution of Calixarenes: Carboxylic Acids
  作者：Shiv Kumar Sharma、Suseela Kanamathareddy、C. David Gutsche

  DOI：10.1055/s-1997-1359

  日期：1997.11

  The mono- (5a), bis- (4a and 4b), and tetrakis (1a)-p-cyanomethylcalix[4]arenes as well as the bis(cyanomethyl)calix[6]arene (6a) have been transformed both by acid and base induced hydrolysis to the corresponding p-carboxymethylcalix[4]arenes 5b, 4c, 4d, 2a, and 6b which, in turn, were converted to the methyl (5c, 4e, 4f, 2b) and ethyl (5d, 4g, 2c) esters. The cyanomethyl groups in the sterically hindered compounds 7 and 8 and their corresponding monomers 10 and 11, however, were inert to hydrolysis, even under strenuous conditions. The methyl ester 2b can be converted to the 1,3-dibenzyl ether (3b) and the 1,3-dibenzoate (3c) as well as the tetrabenzyl ether (3a) and tetrabenzoate (3d).

  单取代（5a）、双取代（4a 和 4b）以及四取代（1a）对位氰基甲基卡利克斯[4]芳烃和双（氰基甲基）卡利克斯[6]芳烃（6a）经过酸和碱诱导的水解反应，转化为相应的对位羧基甲基卡利克斯[4]芳烃（5b、4c、4d、2a 和 6b），而这些产物又进一步转化为甲酯（5c、4e、4f、2b）和乙酯（5d、4g、2c）。然而，立体障碍化合物 7 和 8 及其对应的单体 10 和 11 中的氰基甲基在严格条件下对此反应表现出惰性，未能发生水解。甲酯 2b 可转化为 1,3-二苄基醚（3b）、1,3-二苄酸酯（3c）、四苄基醚（3a）和四苄酸酯（3d）。
• Synthesis of calix[4]arenes carrying bulky upper-rim groups
  作者：Shiv Kumar Sharma、C.David Gutsche

  DOI：10.1016/s0040-4039(00)73916-5

  日期：1993.1

  NaH-induced arylmethylation of p-cyanomethylcalix[4]arene introduces arylmethyl groups on the phenolic oxygens and the carbons a to the cyano groups to give calixarenes carrying very bulky upper-rim substituents.
• Sharma Shiv Kumar, Gutsche C. David, J. Org. Chem, 59 (1994) N 20, S 6030-6037
  作者：Sharma Shiv Kumar, Gutsche C. David

  DOI：——

  日期：——