5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrahydroxycalix[4]arene monospirodienon | 146923-74-2

• 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: 5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrahydroxycalix[4]arene monospirodienon
• 英文别名: 6,12,18,24-Tetratert-butyl-27,28-dihydroxy-2-oxahexacyclo[20.3.1.11,4.110,14.116,20.03,8]nonacosa-3(8),4,6,10,12,14(28),16(27),17,19,22,24-undecaen-26-one
• CAS: 146923-74-2；145903-47-5
• 化学式: C₄₄H₅₄O₄
• 分子量: 646.91
• InChiKey: KJQAFRXNMZTPIB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.1
• 重原子数：
  48
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrahydroxycalix[4]arene monospirodienon 以60%的产率得到
  参考文献：
  名称：

  Litwak Ariel M., Grynszpan Flavio, Aleksiuk Oleg, Cohen Shmuel, Biali Sil+, J. Org. Chem., 58 (1993) N 2, S 393-402

  摘要：

  DOI：
• 作为产物：
  描述：

  5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix-4-arene 在 Trimethylphenylammonium tribromide 碳酸氢钠 作用下， 以 二氯甲烷 为溶剂， 以20%的产率得到5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrahydroxycalix[4]arene monospirodienon
  参考文献：
  名称：

  Proximal intraannular modifications of calix[4]arene via its spirodienone derivative

  摘要：

  对叔丁基杯[4]芳烃 1 的温和氧化产生手性螺二烯酮 3，其用作制备近端二取代和双脱羟基杯芳烃的中间体； 3的晶体结构已确定。

  DOI：

  10.1039/c39930000011

文献信息

• Proximal intraannular modifications of calix[4]arene via its spirodienone derivative
  作者：Oleg Aleksiuk、Flavio Grynszpan、Silvio E. Biali

  DOI：10.1039/c39930000011

  日期：——

  Mild oxidation of p-tert-butylcalix[4]arene 1 yields the chiral spirodienone 3 which is used as an intermediate for the preparation of proximally disubstituted and didehydroxylated calixarenes; the crystal structure of 3 has been determined.

  对叔丁基杯[4]芳烃 1 的温和氧化产生手性螺二烯酮 3，其用作制备近端二取代和双脱羟基杯芳烃的中间体； 3的晶体结构已确定。
• Preparation, stereochemistry, and reactions of the bis(spirodienone) derivatives of p-tert-butylcalix[4]arene
  作者：Ariel M. Litwak、Flavio Grynszpan、Oleg Aleksiuk、Shmuel Cohen、Silvio E. Biali

  DOI：10.1021/jo00054a023

  日期：1993.1

  The stereochemistry of the spirodienone derivatives of p-tert-butylcalix[4]arene (1) is analyzed. Treatment of 1 with base and 2 equiv of phenyltrimethylammonium tribromide resulted in the formation of a mixture of three main products (4A, 4A', and 4B) each containing two spirodienone moieties. The molecules slowly mutually interconvert in solution, and in toluene at 80-degrees-C the equilibrium mixture is composed of 10% 4A', 65% 4A, and 25% 4B. From the NMR data, it is concluded that both 4A and 4A' are systems in which the two cyclohexadienone groups are at distal positions (1,3) whereas 4B has C(s) symmetry and the cyclohexadienone rings are at proximal (1,2) positions. Unambiguous structural characterization of the systems was achieved by X-ray crystallography which indicates that 4A' is the chiral form (C2 symmetry) while 4A is the meso (C(i)) form. Attempted reduction of 4A resulted in the regeneration of 1. Reaction of 4A with HCl results in chloro-de-tert-butylation of two rings and rearomatization. Reaction of 4A, 4A', and 4B with excess benzyne yielded the corresponding Diels-Alder adducts 10A, 10A', and 10B which do not interconvert in solution. Based on the NMR data it is concluded that for each compound the additions to the two spirodienones occurred with identical diastereofacial discrimination. The Diels-Alder adducts are the first systems in which the phenolic oxygens of a calixarene were converted into nonconjugated ketone groups.
• Cyclization and Reductive Cleavage of Monospirodienone Calix[4]arene Derivatives. Trihydroxy-p-tert-butylcalix[4]arene Revisited
  作者：Flavio Grynszpan、Oleg Aleksiuk、Silvio E. Biali

  DOI：10.1021/jo00087a022

  日期：1994.4

  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.
• Litwak Ariel M., Grynszpan Flavio, Aleksiuk Oleg, Cohen Shmuel, Biali Sil+, J. Org. Chem., 58 (1993) N 2, S 393-402
  作者：Litwak Ariel M., Grynszpan Flavio, Aleksiuk Oleg, Cohen Shmuel, Biali Sil+

  DOI：——

  日期：——
• Conformation and Stereodynamics of Monodioxamethylene Calix[4]arene Derivatives
  作者：Jens Wöhnert、Jörg Brenn、Matthias Stoldt、Oleg Aleksiuk、Flavio Grynszpan、Iris Thondorf、Silvio E. Biali

  DOI：10.1021/jo9720602

  日期：1998.6.1

  Reaction of the monospirodienone derivative of p-tert-butylcalix[4]arene with methylene chloride/base in the presence of a phase transfer catalyst yielded the bridged monodioxamethylene derivative 6 which was characterized by X-ray crystallography. Treatment of 6 with NaBH4 resulted in exo-reduction of the carbonyl group and afforded the spiro alcohol 7, which rearranged thermally to the monodioxamethylene bridged calix[4]arene 3. Calixarene 3 exists in solution (CD2Cl2, 198 K) in three different conformations (a cone form with the dioxocine unit in a distorted boat conformation, and cone and partial cone forms with a boat-chair arrangement of the dioxocine) which interconvert with barriers in the 13.5-14.3 kcal mol(-1) range. Molecular mechanics calculations indicate that the rate-limiting steps for the conformational interconversions of 3 involve transitions of the dioxocine subunit.