5,11,17,23-Tetra-tert-butyl-25,26,27-trihydroxycalix<4>arene | 131276-09-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 5,11,17,23-Tetra-tert-butyl-25,26,27-trihydroxycalix<4>arene
• 英文别名: 5,11,17,23-Tetratert-butylpentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3(28),4,6,9(27),10,12,15,17,19(26),21,23-dodecaene-25,26,27-triol
• CAS: 131276-09-0
• 化学式: C₄₄H₅₆O₃
• 分子量: 632.927
• InChiKey: ZTGYDVLSDCTUMH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.3
• 重原子数：
  47
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  60.7
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5,11,17,23-Tetra-tert-butyl-25,26,27-trihydroxycalix<4>arene 在 phenyltrimethylammonium tribromide 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以19%的产率得到
  参考文献：
  名称：

  Cyclization and Reductive Cleavage of Monospirodienone Calix[4]arene Derivatives. Trihydroxy-p-tert-butylcalix[4]arene Revisited

  摘要：

  The monospirodienone derivative of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrahydroxycalix[4]arene (2) undergoes in the presence of an ammonium tribromide salt a spiroannulation reaction at the alpha-position to the carbonyl. Reaction of 2 with an equimolar amount of LA followed by treatment with a phosphorylating agent yielded a monosubstituted spirodienone. Reductive cleavage of the latter (K/NH3) afforded 5,11,17,23-tetra-tert-butyl-25,26,27-trihydroxycalixarene (10). The structure of 10 was corroborated indirectly by X-ray crystallography of its bromo dispiro derivative 11. It is concluded that the compound obtained by cleavage of the bis(diethyl phosphate) ester derivative 13, and previously described by us as 10, is 5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26-monoaminocalix[4]arene (12). The latter readily forms a tosylate salt in CDCl3 solution. Considering this reassignment, the inversion barriers of several OH-depleted aminocalixarenes and their salts are reexamined.

  DOI：

  10.1021/jo00087a022
• 作为产物：
  描述：

  5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix-4-arene 在 氨 、 potassium carbonate 作用下， 以 四氢呋喃 为溶剂， 生成 5,11,17,23-Tetra-tert-butyl-25,26,27-trihydroxycalix<4>arene
  参考文献：
  名称：

  选择性脱羟基的杯[4]芳烃和1,3-二硫代杯[4]芳烃；杯[4]芳烃的新类别

  摘要：

  杯[4]芳烃的选择性修饰，可以通过磷酸盐的还原去除或通过1,3-双（二甲基硫代氨基甲酰基）杯[4]芳烃的Newman-Kwart重排而进行选择性脱羟基，从而产生杯[4]芳烃3和1,3-二硫杂杯[4]芳烃6。

  DOI：

  10.1039/c39900001432

文献信息

• Synthesis of Novel Tantalacalixarene Complexes: First Example of Intramolecular CH Activation of Monodepleted Aromatic Ring
  作者：Jeff Espinas、Jérémie Pelletier、Erwan Jeanneau、Ulrich Darbost、Kai C. Szeto、Christine Lucas、Jean Thivolle-Cazat、Christian Duchamp、Natali Henriques、Denis Bouchu、Jean-Marie Basset、Henry Chermette、Isabelle Bonnamour、Mostafa Taoufik

  DOI：10.1021/om200140u

  日期：2011.7.11

  by 1H, 13C, NOESY, and COSY spectroscopic studies and single-crystal X-ray diffraction. 7 exhibits unprecedented use of an intramolecular C–H activation of an aromatic ring and simultaneously releases of one equivalent of neopentane. DFT calculation supports a mechanism in which the metal passes through a transition state involving a coplanar arrangement with its three ligands (CAr, HAr, CNp).

  的烷基化（dichlorotantala） - p -叔-butylcalix [4]芳烃1和3通过NpMgCl两个当量（NP =新戊基），得到相应的未报告（bisneopentyltantala） - p -叔-butylcalix [4]芳烃4和5。这些配合物可以通过适度升高温度进行脱烷基化，得到6和7。配合物6和7的表征和结构构象由1 H，13确定C，NOESY和COZY光谱研究和X射线单晶衍射。7展示了对芳香环的分子内C–H活化的空前使用，并同时释放了一当量的新戊烷。DFT计算支持一种机制，其中金属穿过过渡态，该过渡态包括其三个配体（C Ar，H Ar，C Np）的共面排列。
• Conformational isomers of the trimethyl ethers of monodeoxycalix[4]arenes
  作者：Yoshimasa Fukazawa、Kousaku Yoshimura、Shigeru Sasaki、Masumi Yamazaki、Toshiya Okajima

  DOI：10.1016/0040-4020(95)01047-5

  日期：1996.2

  The conformational analysis of title compounds using X-ray crystallographic analysis and molecular mechanics calculations is presented. The (u,u,d) conformer is the most stable among three possible forms. Solvent polarity plays a significant role in its conformational dynamic equilibrium. In the most stable form, the orientation of the methoxyl group of the inverted anisole ring is inside a cavity created by the remaining three aromatic rings as was found in the structure of one of the derivatives in its crystalline state. This cavity filling inward orientation of the alkoxyl group is quite a characteristic feature for the trimethyl ethers of the monodeoxycalix[4]arenes.
• Selective hydroxyl replacement in calixarenes: amino-, azo-, and xanthenocalixarene derivatives.
  作者：Oleg Aleksiuk、Shmuel Cohen、Silvio E. Biali

  DOI：10.1021/ja00143a005

  日期：1995.9

  The synthesis of monoamino-, azo-, and xanthenocalixarenes and dehydroxylated calixarenes via condensation, reduction, or rearrangement of monospirodienone calixarene derivatives is described. Mild oxidation of p-tert-butylcalix[5]arene and p-tert-butylcalix[6]arene yielded their corresponding monospirodienone derivatives 4b and 4c. Monospirodienone 4b was characterized by X-ray crystallography. Reaction of 4b with (2,4-dinitrophenyl)hydrazine gave a (dinitrophenyl)azo derivative (8), which by reaction with HI gave the monoaminotetrahydroxycalix[5]arene 10. Reaction of 4b with hydrazine/base yielded in a Wolff-Kishner-type reaction, the monodehydroxylated calix[5]arene 8. Reaction of 4b with a methanolic solution of hydrazine at room temperature yielded a derivative characterized by X-ray crystallography as a system with an azo bridge (15). Spirodienone 4b rearranges in MeOH/H+, yielding the xanthene derivative 16 as the main product, together with the linear pentamer 17. The larger spirodienone 4c rearranges by treatment with MeOH/H+, yielding the xanthenocalix[6]arene 18. X-ray diffraction of a crystal of 18 grown in MeCN shows that in the crystal the molecules form intermolecular hydrogen-bonded dimers in which the two molecules mutually include each other; i.e., one of the protuberances of each molecule is located in the V-shaped cavity of its neighboring molecule. Molecules 16 and 18 represent the first examples of calixarene systems incorporating a xanthene moiety.
• TING, YUHUA;VERBOOM, WILLEM;GROENEN, LEO C.;VAN, LOON JAN-DIRK;REINHOUDT,+, J. CHEM. SOC. CHEM. COMMUN.,(1990) N0, C. 1432-1433
  作者：TING, YUHUA、VERBOOM, WILLEM、GROENEN, LEO C.、VAN, LOON JAN-DIRK、REINHOUDT,+

  DOI：——

  日期：——
• GRYNSZPAN, FLAVIO;GOREN, ZAFRIN;BIALI, SILVIO E., J. ORG. CHEM., 56,(1991) N, C. 532-536
  作者：GRYNSZPAN, FLAVIO、GOREN, ZAFRIN、BIALI, SILVIO E.

  DOI：——

  日期：——