6^A-O-(tert-Butyldimethylsilyl)heptakis(2,3-di-O-methyl)-6^B,6^C,6^D,6^E,6^F,6^G-hexa-O-methyl-β-cyclodextrin | 150885-21-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6^A-O-(tert-Butyldimethylsilyl)heptakis(2,3-di-O-methyl)-6^B,6^C,6^D,6^E,6^F,6^G-hexa-O-methyl-β-cyclodextrin
• 英文别名: tert-butyl-dimethyl-[[(1R,3R,5R,6R,8R,10R,11R,13R,15R,16R,18R,20R,21R,23R,25R,26R,28R,30R,31R,33R,35R,36S,37R,38S,39R,40S,41R,42S,43R,44S,45R,46S,47R,48S,49R)-36,37,38,39,40,41,42,43,44,45,46,47,48,49-tetradecamethoxy-5,15,20,25,30,35-hexakis(methoxymethyl)-2,4,7,9,12,14,17,19,22,24,27,29,32,34-tetradecaoxaoctacyclo[31.2.2.23,6.28,11.213,16.218,21.223,26.228,31]nonatetracontan-10-yl]methoxy]silane
• CAS: 150885-21-5
• 化学式: C₆₈H₁₂₄O₃₅Si
• 分子量: 1529.8
• InChiKey: NDEMDSDOFBAIBI-WMWVZREGSA-N

物化性质

• 沸点：
  1133.6±65.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.88
• 重原子数：
  104
• 可旋转键数：
  30
• 环数：
  21.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  323
• 氢给体数：
  0
• 氢受体数：
  35

反应信息

• 作为反应物：
  描述：

  6^A-O-(tert-Butyldimethylsilyl)heptakis(2,3-di-O-methyl)-6^B,6^C,6^D,6^E,6^F,6^G-hexa-O-methyl-β-cyclodextrin 在 氟化铵 作用下， 以 甲醇 为溶剂， 生成 permethylated mono-6-hydroxy-β-cyclodextrin
  参考文献：
  名称：

  Acetylenic cyclodextrins for multireceptor architectures: cups with sticky ends for the formation of extension wires and junctions

  摘要：

  通过两种合成路线制备出了单-6-O-丙炔基过甲基化的 β-环糊精 3，它是一种多功能构筑基块，可用于构建具有潜在电子传导性核结的环糊精二聚体和三聚体。通过格拉塞-海耦合 3 得到了 β-环糊精二聚体 6，而通过钯（0）催化耦合则制备出了具有 1,4-亚苯基桥的环糊精二聚体 7 和基于 1,3,5-三取代苯的环糊精三聚体 8。 所有化合物都经过了全面的表征，特别是通过二维核磁共振光谱技术进行的详细分析为了解化合物的特性提供了有用的信息。此外，还介绍了单-3,6-脱水-庚基（2,3-O-甲基）-己基（6-O-甲基）-β-环糊精 5 的详细全面特性。产物 5 是在化合物 3 的甲基化过程中形成的，其形成对反应条件非常敏感。此外，还报告了与苯连接的二聚体 7 和三聚体 8 的吸收光谱和荧光光谱。它们显示了激发态的不同特性，这是因为苯烯核心施加了不同的电子耦合。

  DOI：

  10.1039/b508607h
• 作为产物：
  描述：

  6-O-(tert-Butyldimethylsilyl)heptakis(2,3-di-O-methyl)-β-cyclodextrin 、 碘甲烷 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以69%的产率得到6^A-O-(tert-Butyldimethylsilyl)heptakis(2,3-di-O-methyl)-6^B,6^C,6^D,6^E,6^F,6^G-hexa-O-methyl-β-cyclodextrin
  参考文献：
  名称：

  New permethyl-substituted .beta.-cyclodextrin polysiloxanes for use as chiral stationary phases in open tubular column chromatography

  摘要：

  Heptakis(2,3-di-O-methyl)-6-O-tosyl-beta-cyclodextrin (2) was prepared from heptakis(2,3-di-O-methyl)-beta-cyclodextrin (1) in a 31 % yield. The tosyl group of 2 was substituted by p-(allyloxy)phenyl in a yield of 74 % to produce 6-O-(p-(allyloxy)phenyl)heptakis(2,3-di-O-methyl)-beta-cyclodextrin (3). This material was derivatized at the other 6-positions to produce persubstituted 6A-O-(p-(allyloxy)phenyl)-beta-cyclodextrins 4, 5, and 8. Permethylated 6-O-tosyl-beta-cyclodextrin 9, which was used for the preparation of 10-12, was obtained from 2 almost quantitatively. 6-O-(tert-Butyldimethylsilyl)-(heptakis(2,3-di-O-methyl)-beta-cyclodextrin (13) was also obtained from 1 in a 33% yield. Permethylated 6A-deoxy-6A-methylene-beta-cyclodextrin (17) was prepared from 13 by a 4-step process. Seven new permethyl-substituted beta-cyclodextrins bound to polymethylsiloxane were prepared by a hydrosilylation reaction of the permethyl-substituted monoalkenyl-beta-cyclodextrins with polyhydromethylsiloxane. The polymeric phases provide excellent enantiomeric separation of a variety of chiral solutes in open tubular column supercritical fluid chromatography (SFC) and gas chromatography (GC).

  DOI：

  10.1021/jo00070a019

文献信息

• Acetylenic cyclodextrins for multireceptor architectures: cups with sticky ends for the formation of extension wires and junctions
  作者：Jonathan A. Faiz、Neil Spencer、Zoe Pikramenou

  DOI：10.1039/b508607h

  日期：——

  A mono-6-O-propargyl permethylated β-cyclodextrin, 3, has been prepared by two synthetic routes as a versatile building block for the construction of cyclodextrin dimers and trimers with a core junction which is potentially electron conducting. Glaser–Hay coupling of 3 gave β-cyclodextrin dimer 6, and Pd(0)-catalysed coupling allowed the preparation of a cyclodextrin dimer with a 1,4-phenylene bridge, 7, and a cyclodextrin trimer based on a 1,3,5-trisubstituted benzene, 8. All compounds have been fully characterised, and in particular, detailed analysis by 2D NMR spectroscopic techniques has provided useful insight into the identities of the compounds. The detailed full characterisation of mono-3,6-anhydro-heptakis(2,3-O-methyl)-hexakis(6-O-methyl)-β-cyclodextrin, 5, is also described. Product 5 is formed during the methylation of compound 3, and its formation was found to be sensitive to the reaction conditions. The absorption and fluorescence spectra of the phenylene-bridged dimer 7 and trimer 8 are also reported. They show different properties of the excited state based on the different electronic coupling imposed by the phenylene core.

  通过两种合成路线制备出了单-6-O-丙炔基过甲基化的 β-环糊精 3，它是一种多功能构筑基块，可用于构建具有潜在电子传导性核结的环糊精二聚体和三聚体。通过格拉塞-海耦合 3 得到了 β-环糊精二聚体 6，而通过钯（0）催化耦合则制备出了具有 1,4-亚苯基桥的环糊精二聚体 7 和基于 1,3,5-三取代苯的环糊精三聚体 8。 所有化合物都经过了全面的表征，特别是通过二维核磁共振光谱技术进行的详细分析为了解化合物的特性提供了有用的信息。此外，还介绍了单-3,6-脱水-庚基（2,3-O-甲基）-己基（6-O-甲基）-β-环糊精 5 的详细全面特性。产物 5 是在化合物 3 的甲基化过程中形成的，其形成对反应条件非常敏感。此外，还报告了与苯连接的二聚体 7 和三聚体 8 的吸收光谱和荧光光谱。它们显示了激发态的不同特性，这是因为苯烯核心施加了不同的电子耦合。
• A convenient synthesis of mono-6-hydroxy permethylated β-cyclodextrin via tert-butyldimethylsilylation
  作者：Zhen Chen、Jerald S Bradshaw、Milton L Lee

  DOI：10.1016/0040-4039(96)01545-6

  日期：1996.9

  A convenient method to prepare mono-6-hydroxy permethylated β-cyclodextrin (3) viatert-butyldimethylsilylation is described. Mono-6-tert-butyldimethylsilyl-β-cyclodextrin was prepared and treated with NaH and CH3I in the same pot. The protecting group was removed by refluxing with NH4F in CH3OH to give 3 in an overall yield of 43%.

  描述了一种通过叔丁基二甲基甲硅烷基化制备单6-羟基过甲基化的β-环糊精（3）的简便方法。制备单-6-叔丁基二甲基甲硅烷基-β-环糊精，并在同一罐中用NaH和CH 3 I处理。通过与NH 4 F在CH 3 OH中的回流来除去保护基，以总产率43％得到3。
• Selective access and full characterization of mono-acidic permethylated β-cyclodextrin derivatives and their methyl esters
  作者：S. Tisse、V. Peulon-Agasse、H. Oulyadi、F. Marsais、J.C. Combret

  DOI：10.1016/s0957-4166(03)00446-4

  日期：2003.8

  Three acidic derivatives of permethylated beta-cyclodextrin, 2(I)-O-carboxymethyl-2(II-VII),3(I-VII),6(I-VII)-eicosa-O-methyl-cyclomaltoheptaose, 6(I)-O-carboxymethyl-2(I-VII),3(I-VII),6(II-VII)-eicosa-O-methyl-cyclomaltoheptaose, 6(I)-desoxy-6(I)-carboxy-2(I-VII),3(I-III),6(II-VII)-eicosa-O-methyl-cyclomaltoheptaose and the corresponding methyl esters have been synthesized with good yields starting from mono-hydroxy permethylated beta-CD prepared via tert-butyldimethylsilyl protection in 6-position and p-methoxybenzyl protection at the 2-position. All of these compounds were fully characterized by high field H-1 and C-13 NMR and HPLC/MS. (C) 2003 Elsevier Ltd. All rights reserved.
• New permethyl-substituted .beta.-cyclodextrin polysiloxanes for use as chiral stationary phases in open tubular column chromatography
  作者：Guoliang Yi、Jerald S. Bradshaw、Bryant E. Rossiter、Abdul Malik、Wenbao Li、Patrik Petersson、Karin E. Markides、Milton L. Lee

  DOI：10.1021/jo00070a019

  日期：1993.8

  Heptakis(2,3-di-O-methyl)-6-O-tosyl-beta-cyclodextrin (2) was prepared from heptakis(2,3-di-O-methyl)-beta-cyclodextrin (1) in a 31 % yield. The tosyl group of 2 was substituted by p-(allyloxy)phenyl in a yield of 74 % to produce 6-O-(p-(allyloxy)phenyl)heptakis(2,3-di-O-methyl)-beta-cyclodextrin (3). This material was derivatized at the other 6-positions to produce persubstituted 6A-O-(p-(allyloxy)phenyl)-beta-cyclodextrins 4, 5, and 8. Permethylated 6-O-tosyl-beta-cyclodextrin 9, which was used for the preparation of 10-12, was obtained from 2 almost quantitatively. 6-O-(tert-Butyldimethylsilyl)-(heptakis(2,3-di-O-methyl)-beta-cyclodextrin (13) was also obtained from 1 in a 33% yield. Permethylated 6A-deoxy-6A-methylene-beta-cyclodextrin (17) was prepared from 13 by a 4-step process. Seven new permethyl-substituted beta-cyclodextrins bound to polymethylsiloxane were prepared by a hydrosilylation reaction of the permethyl-substituted monoalkenyl-beta-cyclodextrins with polyhydromethylsiloxane. The polymeric phases provide excellent enantiomeric separation of a variety of chiral solutes in open tubular column supercritical fluid chromatography (SFC) and gas chromatography (GC).
• Cyclodextrin-Based Ionic Liquids as Enantioselective Stationary Phases in Gas Chromatography
  作者：Nuno Costa、Sara Matos、Marco D. R. Gomes da Silva、M. Manuela A. Pereira

  DOI：10.1002/cplu.201300229

  日期：2013.12

  te ionic liquids were synthesized from the corresponding permethylated mono-6-hydroxycyclodextrins in a one-pot reaction and solvent-free procedure. Regioselective transformation of native α- and β-cyclodextrins with the use of a bulky tert-butyldiphenylsilyl protecting group afforded the desired 6-monosubstituted permethylated cyclodextrin derivatives in moderate yields. The new ionic liquids were

  合成了新的全甲基化的单-6-脱氧-6-吡啶-1-鎓和单-6-脱氧-6-（1-乙烯基-1H-咪唑-3-鎓）-α-和-β-环糊精三氟甲磺酸盐离子液体。一锅反应和无溶剂方法从相应的全甲基化的单-6-羟基环糊精中纯化得到。使用大的叔丁基二苯基甲硅烷基保护基对天然α-和β-环糊精进行区域选择性转化，以中等收率得到了所需的6-单取代的全甲基化的环糊精衍生物。在毛细管气相色谱柱中将新的离子液体作为固定相进行测试，以进行外消旋混合物的对映体-气相色谱分析中的手性鉴别。全甲基化的6-脱氧-6-吡啶-1-基-α-环糊精三氟甲磺酸盐显示出一些消旋酯和内酯以及环氧化物的良好对映异构体分离。