3,9,17,23-Tetratert-butyl-13,27-dioxa-6,20,29,30-tetrathiaheptacyclo[23.3.1.111,15.05,28.07,12.014,19.021,26]triaconta-1,3,5(28),7(12),8,10,14(19),15,17,21(26),22,24-dodecaene | 950778-64-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噻嗪类
• 英文名称: 3,9,17,23-Tetratert-butyl-13,27-dioxa-6,20,29,30-tetrathiaheptacyclo[23.3.1.111,15.05,28.07,12.014,19.021,26]triaconta-1,3,5(28),7(12),8,10,14(19),15,17,21(26),22,24-dodecaene
• CAS: 950778-64-0
• 化学式: C₄₀H₄₄O₂S₄
• 分子量: 685.052
• InChiKey: MDOOWFWZUXENHQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.2
• 重原子数：
  46
• 可旋转键数：
  4
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  120
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,9,17,23-Tetratert-butyl-13,27-dioxa-6,20,29,30-tetrathiaheptacyclo[23.3.1.111,15.05,28.07,12.014,19.021,26]triaconta-1,3,5(28),7(12),8,10,14(19),15,17,21(26),22,24-dodecaene 在 aluminum (III) chloride 、 苯酚 作用下， 以 甲苯 为溶剂， 反应 192.0h， 以26%的产率得到13,27-Dioxa-6,20,29,30-tetrathiaheptacyclo[23.3.1.111,15.05,28.07,12.014,19.021,26]triaconta-1,3,5(28),7(12),8,10,14(19),15,17,21(26),22,24-dodecaene
  参考文献：
  名称：

  Reactions of thiacalix[4]arene 1,3-bistriflate: formation of thiacalix[2]phenoxathiins—structural and complexation studies

  摘要：

  硫杂[4]炔 2 的 1,3-二三叉酯在各种条件下（包括典型的 Sonogashira 和其他基本条件）与 CuI 反应，产生了水解和重排产物的混合物，其中包括 Hattori 及其合作者也报道过的双(吩噁噻)3。据报道，一种前所未有的窄边三酸酯被一个氢原子置换，形成了一种新的部分共硫杂堇青霉烯 2i，同时还发现了五种新的 X 射线晶体结构。从 3 合成了去叔丁基类似物 3a，并报道了它们与 Ag+ 和 Hg2+ 的络合性质。

  DOI：

  10.1039/b801483c
• 作为产物：
  描述：

  [5,11,17,23-Tetratert-butyl-26,28-dihydroxy-27-(trifluoromethylsulfonyloxy)-2,8,14,20-tetrathiapentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaen-25-yl] trifluoromethanesulfonate 在 copper(l) iodide 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以68%的产率得到3,9,17,23-Tetratert-butyl-13,27-dioxa-6,20,29,30-tetrathiaheptacyclo[23.3.1.111,15.05,28.07,12.014,19.021,26]triaconta-1,3,5(28),7(12),8,10,14(19),15,17,21(26),22,24-dodecaene
  参考文献：
  名称：

  Ullmann coupling reaction of 1,3-bistriflate esters of calix[4]arenes: facile syntheses of monoaminocalix[4]arenes and 4,4′:6,6′-diepithiobis(phenoxathiine)

  摘要：

  Treatment of 1,3-bistriflate esters of thiacalix- (6a) and calix[4]arenes 6b with benzylamine in the presence of Cul and K3PO4 results in the displacement of a TfO moiety with a benzylamino group, which provides an easy access to monoaminothiacalix(4]arene 4a and its methylene-bridged counterpart 4b. On the other hand, the reaction of 6a in the absence of benzylamine leads to intramolecular dietherification, giving 4,4':6,6'-diepithiobis(phenoxathiine) 7a. (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.08.095

文献信息

• Synthesis of Mono- and 1,3-Diaminocalix[4]arenes via Ullmann-Type Amination and Amidation of 1,3-Bistriflate Esters of Calix[4]arenes
  作者：Yuka Nakamura、Shinya Tanaka、Ryuichi Serizawa、Naoya Morohashi、Tetsutaro Hattori

  DOI：10.1021/jo102566e

  日期：2011.4.1

  instead of the hydroxy group(s) at the 28-position or at both the 26- and 28-positions of p-tert-butylcalix[4]arene (1a) and p-tert-butylthiacalix[4]arene (1b), via the Ullmann-type amination or amidation. Thus, the copper-catalyzed or mediated amination of the 1,3-bistriflate ester (2a) of 1a with benzylamine affords either mono(benzylamino) triflate 7a or 1,3-bis(benzylamine) 8 in a high yield, depending

  描述了用于制备单胺4和1，3-二胺5的实用方法，所述单胺4和1，3-二胺5在28位或在26位和28位都带有一个或两个氨基而不是羟基的p -叔-butylcalix [4]芳烃（1A）和p -叔-butylthiacalix [4]芳烃（1B），通过乌尔曼型胺化或酰胺化。因此，用苄胺对1a的1，3-二rifriflate酯（2a）进行铜催化或介导的胺化反应可得到单（苄基氨基）三氟甲磺酸酯7a或1，3-双（苄基胺）8。取决于反应条件，产率高。另一方面，1b的1，3-二rifriflate酯（2b）抵抗分解并且在化学计量条件下产生三氟甲磺酸单（苄基氨基）7b。的二取代2B是通过酰胺化与甲苯磺酰胺来实现，得到1,3-双（甲苯磺酰胺）17B。7a的苄氨基部分的氢解，然后Tf部分的水解，得到单胺4a，而8的氢解得到1,3-二胺5a。7b的氨基部分可以在酸性条件下脱保护，在水解后得到单胺4b。17b的水
• Intramolecular rearrangement of 1,3-bistriflate ester of thiacalix[4]arene to 1,2-counterpart: an efficient di-O-protection method for the stereoselective synthesis of anti-1,2-diethers
  作者：Ryuichi Serizawa、Shinya Tanaka、Naoya Morohashi、Fumitaka Narumi、Tetsutaro Hattori

  DOI：10.1016/j.tetlet.2007.07.025

  日期：2007.9

  anti-selective dialkylation of the proximal hydroxy groups of thiacalix[4]arene 2 is achieved for the first time via the initial protection of the two proximal hydroxy groups of compound 2 with Tf moieties by intramolecular rearrangement of easily preparable 1,3-bistriflate ester 3 to 1,2-counterpart 4, followed by anti-selective dialkylation of the remaining hydroxy groups with alkyl halides or under the Mitsunobu

  通过容易制备的1,3-分子内重排，通过Tf部分对化合物2的两个近端羟基进行初始保护，首次实现了噻唑烷[4]亚芳基2的近端羟基的净抗选择性二烷基化。将3酯化为1,2-对位4，然后用卤代烷或在Mitsunobu条件下对剩余的羟基进行反选择性二烷基化，然后除去Tf部分。
• Ullmann coupling reaction of 1,3-bistriflate esters of calix[4]arenes: facile syntheses of monoaminocalix[4]arenes and 4,4′:6,6′-diepithiobis(phenoxathiine)
  作者：Shinya Tanaka、Ryuichi Serizawa、Naoya Morohashi、Tetsutaro Hattori

  DOI：10.1016/j.tetlet.2007.08.095

  日期：2007.10

  Treatment of 1,3-bistriflate esters of thiacalix- (6a) and calix[4]arenes 6b with benzylamine in the presence of Cul and K3PO4 results in the displacement of a TfO moiety with a benzylamino group, which provides an easy access to monoaminothiacalix(4]arene 4a and its methylene-bridged counterpart 4b. On the other hand, the reaction of 6a in the absence of benzylamine leads to intramolecular dietherification, giving 4,4':6,6'-diepithiobis(phenoxathiine) 7a. (C) 2007 Elsevier Ltd. All rights reserved.
• Reactions of thiacalix[4]arene 1,3-bistriflate: formation of thiacalix[2]phenoxathiins—structural and complexation studies
  作者：Almeqdad Habashneh、Chester R. Jablonski、Julie Collins、Paris E. Georghiou

  DOI：10.1039/b801483c

  日期：——

  Reaction of the 1,3-bistriflate of thiacalix[4]arene 2 under various conditions including typical Sonogashira and other basic conditions with CuI, afforded a mixture of hydrolysis and rearrangement products including a bis(phenoxathiin) 3 reported also by Hattori and co-workers. An unprecedented displacement of a narrow-rim triflate by a hydrogen atom to form a new partial conethiacalixarene 2i is reported as are five new X-ray crystal structures. The de-tert-butylated analogue 3a was synthesized from 3 and their complexation properties with Ag+ and Hg2+ are also reported.

  硫杂[4]炔 2 的 1,3-二三叉酯在各种条件下（包括典型的 Sonogashira 和其他基本条件）与 CuI 反应，产生了水解和重排产物的混合物，其中包括 Hattori 及其合作者也报道过的双(吩噁噻)3。据报道，一种前所未有的窄边三酸酯被一个氢原子置换，形成了一种新的部分共硫杂堇青霉烯 2i，同时还发现了五种新的 X 射线晶体结构。从 3 合成了去叔丁基类似物 3a，并报道了它们与 Ag+ 和 Hg2+ 的络合性质。