2,8,13,19-Tetrakis(1,1-dimethylethyl)-11H,22H-4,6:6,10:15,17:17,21-tetramethanodibenzo<1,10>dioxacyclooctadecin-23,25-dione | 145986-91-0

• 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: 2,8,13,19-Tetrakis(1,1-dimethylethyl)-11H,22H-4,6:6,10:15,17:17,21-tetramethanodibenzo<1,10>dioxacyclooctadecin-23,25-dione
• 英文别名: (1S,14R)-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
• CAS: 145986-91-0
• 化学式: C₄₄H₅₂O₄
• 分子量: 644.894
• InChiKey: HZTIWTSXJJCVAG-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：

  2,8,13,19-Tetrakis(1,1-dimethylethyl)-11H,22H-4,6:6,10:15,17:17,21-tetramethanodibenzo<1,10>dioxacyclooctadecin-23,25-dione 在 盐酸 作用下， 以 乙腈 为溶剂， 反应 0.67h， 以53%的产率得到11,23-Di-tert-butyl-5,17-dichloro-25,26,27,28-tetrahydroxycalix<4>arene
  参考文献：
  名称：

  Preparation, stereochemistry, and reactions of the bis(spirodienone) derivatives of p-tert-butylcalix[4]arene

  摘要：

  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.

  DOI：

  10.1021/jo00054a023
• 作为产物：
  描述：

  5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix-4-arene 以27%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

• Calix[4]bis(spirodienone) as a versatile synthon for upper rim alkoxylation of calixarenes and synthesis of novel triazole-based biscalixarene by ‘CuAAC’ chemistry
  作者：Sreeja Thulasi、Anupriya Savithri、Ramavarma Luxmi Varma

  DOI：10.1080/10610278.2011.556252

  日期：2011.7.1

  alcohols employing a novel ipso nucleophilic substitution of tert-butyl groups by alkoxy groups. Additionally, a route has been paved towards the preparation of triazole-linked biscalixarene via the copper(I)-catalysed modern version of classical Huisgen 1,3-dipolar cycloaddition of alkynyl calixarene and azidocalixarene, derived from the above-mentioned bromo-substituted calixarene.

  杯[4]双（螺二烯酮）的螺环已经使用各种溴官能化醇被打开，采用了叔丁基被烷氧基的新型同位亲核取代。此外，通过铜（I）催化的现代版本的炔基杯芳烃和叠氮杯芳烃（衍生自上述溴取代杯芳烃）的经典 Huisgen 1,3-偶极环加成，为制备三唑连接的双杯芳烃铺平了道路.
• A novel method for the upper rim alkoxy-substitution of calix[4]arene via a bis(spirodienone) route
  作者：Sreeja Thulasi、Ganga V. Bhagavathy、Jijy Eliyan、Luxmi R. Varma

  DOI：10.1016/j.tetlet.2008.11.118

  日期：2009.2

  A mild and efficient one-step procedure for the upper rim modification of calix[4]arene via a bis(spirodienone) is described. The bis(spirodienone) on reaction with alcohols in the presence of p-TSA affords mono- and 1,3-disubstituted alkoxy derivatives in moderate to good yields.

  描述了一种通过双（螺二烯酮）对杯[4]芳烃的上边缘进行修饰的温和有效的一步步骤。在对-TSA存在下与醇反应的双（螺二烯酮）以中等至良好的产率提供单-和1，3-二取代的烷氧基衍生物。
• Direct access to upper rim substituted mono- and diaryloxy calix[4]arenes via bis(spirodienone) route
  作者：Sreeja Thulasi、Jisha Babu、Adarsh Babukuttannair、Viji Sreemathi、Ramavarma Luxmi Varma

  DOI：10.1016/j.tet.2010.04.021

  日期：2010.7

  A seemingly ipso-like nucleophilic substitution of the upper rim of p-tert-butylcalix[4]arene is accomplished by an indirect method involving calix[4]arene derived bis(spirodienone). This method not only provides both mono and 1,3-diaryloxy calixarenes but also enables the synthesis of upper rim monothio substituted calix[4]arenes. A modification of the methodology can be successfully extended for

  对-叔丁基杯[4]芳烃上缘的一种似ipso的亲核取代是通过一种间接方法完成的，该方法涉及杯[4]芳烃衍生的双（螺二烯酮）。该方法不仅提供了单和1，3-二芳氧基杯芳烃，而且还能够合成上边缘单硫取代的杯芳烃[4]芳烃。该方法的修改可以成功地扩展，以更少的步骤选择性合成在下边缘具有游离羟基的单和1,3-二苯醌杯[4]芳烃。
• Studies on the reactivity of calix[4]arene derived bis(spirodienone) with carbo- and hetero-dienophiles and dichlorocarbene: synthesis of highly functionalized macrocycles
  作者：V.B. Ganga、T. Sreeja、E. Suresh、R. Luxmi Varma

  DOI：10.1016/j.tet.2007.02.100

  日期：2007.5

  Calix[4]arene derived bis(spirodienone) can act as a 4π component in cycloaddition reaction with a variety of carbo- and hetero-dienophiles yielding the bisadducts in excellent to quantitative yields. Bis(spirodienone) also undergoes addition reactions with dichlorocarbene resulting in mono- and bis-dichlorocyclopropyl derived bis(spiroenones) in excellent yields.

  杯[4]芳烃衍生的双（螺二烯酮）可以作为环加成反应中的4π组分，与各种碳-和杂-二烯-亲和体产生双加合物，收率极高，可定量。双（螺二烯酮）还与二氯卡宾进行加成反应，从而以优异的收率得到单-和双-二氯环丙基衍生的双（螺烯酮）。
• Spirodienone Route for the Stereoselective Methylene Functionalization of <i>p-tert</i>-Butylcalix[4]arene
  作者：Kasim Agbaria、Silvio E. Biali

  DOI：10.1021/ja0117480

  日期：2001.12.19

  concomitant bond shifts and expulsion of the bromine atoms. Selective trans monodeuteration of two methylene groups of 1 was achieved by reaction of 5b with NaBD4 followed by aromatization of the labeled spirodienol derivative. Reaction of 5b with RONa/ROH (R = Me, Et) afforded the methylene-substituted bis(spirodienone) derivatives 9a and 9b possessing two trans alkoxy groups. X-ray crystallography of 9b indicated

  描述了对叔丁基杯芳烃 (1a) 的两个远端亚甲基进行区域和立体选择性官能化的新方法。内消旋双（螺二烯酮）杯芳烃衍生物 2a 与溴反应得到四溴化产物 3a，其衍生自溴与二烯亚基的外向 1,4-加成。3a 与 NaOH/CH2Cl2 水溶液的相转移催化反应产生了外型双（环氧化物）杯芳烃衍生物 4。在真空中加热 3a 消除了两个 HBr 分子并提供了保留 C(i) 对称性的产物 (5b)的起始材料。X射线分析表明杯芳烃衍生物5b具有两个E构型的环外双键。杯芳烃 5b 在环外双键处与亲核试剂发生反应，伴随着键位移和溴原子的排出。1 的两个亚甲基的选择性反式单氘化是通过 5b 与 NaBD4 的反应，然后是标记的螺二烯醇衍生物的芳构化来实现的。5b 与 RONa/ROH (R = Me, Et) 反应得到亚甲基取代的双（螺二烯酮）衍生物 9a 和 9b，其具有两个反式烷氧基。9b 的 X 射线晶体学