6,12,19,25-Tetratert-butyl-2,16-dioxaheptacyclo[21.3.1.11,4.114,17.117,21.03,8.010,15]triaconta-3(8),4,6,10(15),11,13,18,20,23,25-decaene-27,28-dione | 138899-87-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 香豆素
• 英文名称: 6,12,19,25-Tetratert-butyl-2,16-dioxaheptacyclo[21.3.1.11,4.114,17.117,21.03,8.010,15]triaconta-3(8),4,6,10(15),11,13,18,20,23,25-decaene-27,28-dione
• CAS: 138899-87-3
• 化学式: C₄₄H₅₂O₄
• 分子量: 644.894
• InChiKey: QCNKSWGNHCFPQZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.2
• 重原子数：
  48
• 可旋转键数：
  4
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  6,12,19,25-Tetratert-butyl-2,16-dioxaheptacyclo[21.3.1.11,4.114,17.117,21.03,8.010,15]triaconta-3(8),4,6,10(15),11,13,18,20,23,25-decaene-27,28-dione 以 乙腈 为溶剂， 反应 3.0h， 以50%的产率得到5,12,19,25-Tetratert-butyl-27-hydroxy-9,15-dioxaheptacyclo[21.3.1.17,10.110,13.114,17.03,8.016,21]triaconta-1(26),3(8),4,6,11,14(28),16(21),17,19,23(27),24-undecaen-29-one
  参考文献：
  名称：

  杯[4]芳烃衍生的双（spirodienones）的光化学重排：一个新的大环的形成。

  摘要：

  杯[4]芳烃的双（螺二烯酮）经历了容易的光化学重排，导致了一个新的大环，该大环具有螺环式环戊烯酮-THF单元，三取代的苯酚和苯并呋喃部分。大环系统具有14个成员的不规则腔，类似于固态的部分碗状。

  DOI：

  10.1021/jo062231f
• 作为产物：
  描述：

  5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix-4-arene 在 tetra-N-butylammonium tribromide sodium hydroxide 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 以30%的产率得到6,12,19,25-Tetratert-butyl-2,15-dioxaheptacyclo[21.3.1.11,4.110,14.114,17.03,8.016,21]triaconta-3(8),4,6,10,12,16(21),17,19,23,25-decaene-27,29-dione
  参考文献：
  名称：

  Oxidative cyclization of calix[4]arenes

  摘要：

  p-tert-Butylcalix[4]arene was converted in a single step into a system containing carbonyl and ether binding groups.

  DOI：

  10.1021/jo00033a001

文献信息

• Partial OH → Me Replacement in the Calixarene Scaffold:  Preparation, Conformation, and Stereodynamics of Tetra-<i>tert</i>-butyl-25,27-dihydroxy-26,28-dimethylcalix[4]arene and Its Dimethyl Ether Derivative
  作者：Joel M. Van Gelder、Jörg Brenn、Iris Thondorf、Silvio E. Biali

  DOI：10.1021/jo9623797

  日期：1997.5.1

  The first example of the replacement of hydroxyl groups of a calixarene by methyls is described. Reaction of the bis(spirodienone) calixarene derivative 3B with MeLi afforded the bis addition product 4 which is derived, as shown by X-ray crystallography, from attack on the face of the carbonyls which is anti to the ether oxygen. The reaction of the alternant bis(spirodienone) calixarene derivative 3A with excess MeLi resulted in addition to the C=O groups, but with a concomitant cleavage of the spiro bonds. Ionic hydrogenation (CF3COOH/Et3SiH) of this product (5) yielded 5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26,28-dimethycalix[4]arene (6) while ionic hydrogenation of 4 resulted in fragmentation of the macrocyclic ring. Calixarene 6 adopts a 1,3-alternate conformation both in solution and in the solid state. 6 is conformationally flexible, and an inversion barrier of 15.1 kcal mol(-1) was measured for it by DNMR. The dimethyl ether derivative of 6 (i.e., 7) exists in a partial cone (pace) conformation and undergoes two distinct dynamic processes possessing barriers of 13.3 and 18.1 kcalmol(-1). Molecular mechanics calculations predict correctly the preferred conformation of 6 and 7 and indicate that the topomerization pathways resulting in the mutual exchange of the protons within a methylene group are the following: 1,3-alt --> paco(CH3) --> 1,2-alt --> paco(CH3)* --> 1,3-alt* for 6, and paco(CH3) --> 1,3-alt --> paco(OCH3) --> 1,2 alt --> paco(OCH3)* --> 1,3-alt* --> paco(CH3)* for 7 with calculated barriers of 15.0 and 16.1 kcal mol-l, respectively.
• Oxidative cyclization of calix[4]arenes
  作者：Ariel M. Litwak、Silvio E. Biali

  DOI：10.1021/jo00033a001

  日期：1992.3

  p-tert-Butylcalix[4]arene was converted in a single step into a system containing carbonyl and ether binding groups.
• Photochemical Rearrangement of Calix[4]arene-Derived Bis(spirodienones):  Formation of a New Macrocycle
  作者：Ramavarma Luxmi Varma、Viswanathan Bhagavathy Ganga、Eringathodi Suresh

  DOI：10.1021/jo062231f

  日期：2007.2.1

  Bis(spirodienones) of calix[4]arene undergo a facile photochemical rearrangement leading to a new macrocycle having a spirocyclic cyclopentenone−THF unit, a trisubstituted phenol, and a benzofuran moiety. The macrocyclic ring system has a 14-membered irregular cavity and resembles a partial bowl in the solid state.

  杯[4]芳烃的双（螺二烯酮）经历了容易的光化学重排，导致了一个新的大环，该大环具有螺环式环戊烯酮-THF单元，三取代的苯酚和苯并呋喃部分。大环系统具有14个成员的不规则腔，类似于固态的部分碗状。