(1S,17R)-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 | 145986-93-2

• 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: (1S,17R)-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: 145986-93-2
• 化学式: C₄₄H₅₂O₄
• 分子量: 644.894
• InChiKey: QCNKSWGNHCFPQZ-PIYFIQLCSA-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：

  (1S,17R)-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50%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 以9%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：

文献信息

• Extraannular Fluorinated Calixarenes:  Regiospecificity of the Deoxofluorination Reactions of Bis(spirodienol) Derivatives
  作者：Kasim Agbaria、Jens Wöhnert、Silvio E. Biali

  DOI：10.1021/jo010509s

  日期：2001.10.1

  A new route for the partial displacement of OH groups of p-tert-butylcalixarene via spirodienol derivatives is described. NaBH(4) reduction of the bis(spirodienone) calixarene derivatives 2a-2c afforded the corresponding bis(spirodienols) 3a-3c in stereospecific fashion. (1)H NMR NOESY spectroscopy indicated that in the case of 2a, the reaction proceeds by attack at the exo face of the two carbonyls

  描述了通过螺二烯醇衍生物部分取代对叔丁基杯芳烃的OH基的新途径。双（螺二烯酮）杯芳烃衍生物2a-2c的NaBH（4）还原以立体定向方式提供了相应的双（螺二烯醇）3a-3c。（1）1 H NMR NOESY光谱表明，在2a的情况下，反应是通过在两个羰基的外表面（抗螺旋CO键的表面）上的进攻而进行的。加热时，螺二烯醇很容易还原为对叔丁基杯[4]芳烃。3a与脱氧氟化剂DAST（Et（2）NSF（3））的反应提供了具有一个或两个氟取代的脱羟基环的环外取代的杯芳烃的混合物。双氟化杯芳烃6a在晶体中采用构象（1，3-替代物）类似于二脱羟基杯芳烃6b在溶液中采用的方法。用选择性氘代的螺二烯醇衍生物进行的实验表明，脱氧氟化反应涉及在戊二烯醇亚基的γ位上的区域特异性亲核攻击。
• 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.
• Diels–Alder reactions of bis(spirodienone) derivatives of calix[4]arene with acetylenes: highly regio- and stereoselective synthesis of bisbicyclo[2.2.2]octenone derivatives
  作者：R. Luxmi Varma、V.B. Ganga、E. Suresh

  DOI：10.1016/j.tetlet.2005.03.010

  日期：2005.4

  Highly regio- and stereoselective Diels-Alder reactions of bis(spirodienone) derivatives of calix[4]arene with acetylenes that provide easy access to bisbicyclo[2.2.2]octenones are described. (c) 2005 Elsevier Ltd. All rights reserved.
• 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：——
• Structure and Equilibration Studies of Bis- and Tris(spirodienone) Derivatives of Medium-Sized Calixarenes
  作者：Flavio Grynszpan、Silvio E. Biali

  DOI：10.1021/jo961358+

  日期：1996.1.1

  The isomerism of the tris(spirodienone) derivatives of p-tert-butylcalix[6]arene and bis(spirodienone) derivatives of p-tert-butylcalix[5]arene is analyzed. Oxidation of p-tert-butylcalix[6]arene with phenyltrimethylammonium tribromide/base afforded two chiral tris(spirodienone) calix[6]arene derivatives (3 and 4) which react with excess benzyne yielding the corresponding alb-exo tris adducts 5 and 6. The structural characterization of the tris(spirodienone) derivatives was achieved by 2D NMR methods and in the case of 3, by X-ray crystallography. The main product 3 possess an alternant disposition of the ether and carbonyl functional groups and three spiro stereocenters of dissimilar configurations (RRS/SSR), while the disposition of the functional groups in 4 is nonalternant. Equilibration studies in toluene at 85 degrees C indicate that 3 is the thermodynamically most stable isomer. The tris adduct 5 exists in two nearly equally populated conformations which interconvert with a barrier of 12.1 +/- 0.2 kcal mol(-1). A bis(spirodienone) derivative of p-tert-butylcalix[5]arene was synthesized by oxidation (K3Fe(CN)6/base) of the corresponding monospirodienone derivative. The product obtained is more likely the cycloenantiomeric pair which isomerizes in toluene solution to an isomeric mixture consisting mainly of a heterodirectional isomer of Ct symmetry.