5,11,17,23-tetra-tert-butyl-26,28-dimethoxypentacyclo[19.3.1.1^3,7.1^9,13.1^15,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecane-25,27-dicarbaldehyde

• 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-26,28-dimethoxypentacyclo[19.3.1.1^3,7.1^9,13.1^15,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecane-25,27-dicarbaldehyde
• 英文别名: 5,11,17,23-Tetratert-butyl-26,28-dimethoxypentacyclo[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-25,27-dicarbaldehyde；5,11,17,23-tetratert-butyl-26,28-dimethoxypentacyclo[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-25,27-dicarbaldehyde
• 化学式: C₄₈H₆₀O₄
• 分子量: 701.002
• InChiKey: CHMQMNQZBMOWKF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.2
• 重原子数：
  52
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  52.6
• 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-26,28-dimethoxypentacyclo[19.3.1.1^3,7.1^9,13.1^15,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecane-25,27-dicarbaldehyde 在 1-辛硫醇 、 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 2.0h， 以91%的产率得到5,11,17,23-Tetra-tert-butyl-26,28-dihydroxypentacyclo[19.3.1.1^3,7.1^9,13.1^15,19]octacosa-1(25),3,5, 7(28),9,11,13(27),15,17,19(26),21,23-dodecane-25,27-dicarbaldehyde
  参考文献：
  名称：

  1,3-Diiodocalix[4]arene: Synthesis by Ullmann-Type Iodination of 1,3-Bistriflate Ester of Calix[4]arene, Conformational Analysis, and Transformation into 1,3-Dicarboxy-, Diformyl-, and Dialkylcalix[4]arenes

  摘要：

  A facile synthesis of 1,3-diiodocalix[4]arene 6 has been achieved by copper-catalyzed iodination of the 1,3-bistriflate ester 2a of p-tert-butylcalix[4]arene. After protection of the hydroxy groups with iodomethane, diiodide 6 is subjected to halogenlithium exchange with butyllithium, followed by carbonation with CO2 or formylation with N-formylpiperidine and subsequent deprotection of the hydroxy groups to give novel dicarboxylic acid 11 or dialdehyde 16 in practical yields. The iodo groups of diiodide 6 pass through the calixarene macrocycle; the activation free energy for the conversion of the more stable syn conformer 6syn to the less stable anti conformer 6anti is Delta G(double dagger =) = 104 kJ mol(-1) at 298 K. Dialdehyde 16 shows fast self-exchange between two equivalent species with a cone conformation, Delta G(double dagger), being 63.2 kJ mol1. Dicarboxylic acid 11 adopts a cone conformation and forms a dimer in solution as suggested by 1H NMR and X-ray crystallographic analyses. The arrangement of the iodide groups of compound 6 can be fixed predominantly to anti (17a and 17b) by introducing bulky alkyl groups (e.g., propyl groups) onto the hydroxy groups. The stereospecific alkylation of the iodo groups of the resulting di-O-alkylated anti-1,3-diiodides provides access to the anti-1,3-dialkylcalixarenes 19, which is otherwise difficult to obtain.

  DOI：

  10.1021/jo502563z
• 作为产物：
  描述：

  1-甲酰吡咯烷 、 5,11,17,23-tetra-tert-butyl-25,27-diiodo-26,28-dimethoxypentacyclo[19.3.1.1^3,7.1^9,13.1^15,19]octacosa-1(25),3,5,7(28),9, 11,13(27),15,17,19(26),21,23-dodecane 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以42%的产率得到5,11,17,23-tetra-tert-butyl-26,28-dimethoxypentacyclo[19.3.1.1^3,7.1^9,13.1^15,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecane-25-carbaldehyde
  参考文献：
  名称：

  1,3-Diiodocalix[4]arene: Synthesis by Ullmann-Type Iodination of 1,3-Bistriflate Ester of Calix[4]arene, Conformational Analysis, and Transformation into 1,3-Dicarboxy-, Diformyl-, and Dialkylcalix[4]arenes

  摘要：

  A facile synthesis of 1,3-diiodocalix[4]arene 6 has been achieved by copper-catalyzed iodination of the 1,3-bistriflate ester 2a of p-tert-butylcalix[4]arene. After protection of the hydroxy groups with iodomethane, diiodide 6 is subjected to halogenlithium exchange with butyllithium, followed by carbonation with CO2 or formylation with N-formylpiperidine and subsequent deprotection of the hydroxy groups to give novel dicarboxylic acid 11 or dialdehyde 16 in practical yields. The iodo groups of diiodide 6 pass through the calixarene macrocycle; the activation free energy for the conversion of the more stable syn conformer 6syn to the less stable anti conformer 6anti is Delta G(double dagger =) = 104 kJ mol(-1) at 298 K. Dialdehyde 16 shows fast self-exchange between two equivalent species with a cone conformation, Delta G(double dagger), being 63.2 kJ mol1. Dicarboxylic acid 11 adopts a cone conformation and forms a dimer in solution as suggested by 1H NMR and X-ray crystallographic analyses. The arrangement of the iodide groups of compound 6 can be fixed predominantly to anti (17a and 17b) by introducing bulky alkyl groups (e.g., propyl groups) onto the hydroxy groups. The stereospecific alkylation of the iodo groups of the resulting di-O-alkylated anti-1,3-diiodides provides access to the anti-1,3-dialkylcalixarenes 19, which is otherwise difficult to obtain.

  DOI：

  10.1021/jo502563z

文献信息

• 1,3-Diiodocalix[4]arene: Synthesis by Ullmann-Type Iodination of 1,3-Bistriflate Ester of Calix[4]arene, Conformational Analysis, and Transformation into 1,3-Dicarboxy-, Diformyl-, and Dialkylcalix[4]arenes
  作者：Shinya Tanaka、Takafumi Umetsu、Satoru Nebuya、Naoya Morohashi、Tetsutaro Hattori

  DOI：10.1021/jo502563z

  日期：2015.1.16

  A facile synthesis of 1,3-diiodocalix[4]arene 6 has been achieved by copper-catalyzed iodination of the 1,3-bistriflate ester 2a of p-tert-butylcalix[4]arene. After protection of the hydroxy groups with iodomethane, diiodide 6 is subjected to halogenlithium exchange with butyllithium, followed by carbonation with CO2 or formylation with N-formylpiperidine and subsequent deprotection of the hydroxy groups to give novel dicarboxylic acid 11 or dialdehyde 16 in practical yields. The iodo groups of diiodide 6 pass through the calixarene macrocycle; the activation free energy for the conversion of the more stable syn conformer 6syn to the less stable anti conformer 6anti is Delta G(double dagger =) = 104 kJ mol(-1) at 298 K. Dialdehyde 16 shows fast self-exchange between two equivalent species with a cone conformation, Delta G(double dagger), being 63.2 kJ mol1. Dicarboxylic acid 11 adopts a cone conformation and forms a dimer in solution as suggested by 1H NMR and X-ray crystallographic analyses. The arrangement of the iodide groups of compound 6 can be fixed predominantly to anti (17a and 17b) by introducing bulky alkyl groups (e.g., propyl groups) onto the hydroxy groups. The stereospecific alkylation of the iodo groups of the resulting di-O-alkylated anti-1,3-diiodides provides access to the anti-1,3-dialkylcalixarenes 19, which is otherwise difficult to obtain.