p-(1,1,3,3-tetramethylbutyl)thiacalix[4]arene | 182496-64-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: p-(1,1,3,3-tetramethylbutyl)thiacalix[4]arene
• 英文别名: 15,35,55,75-Tetrakis(2,4,4-trimethylpentan-2-yl)-2,4,6,8-tetrathia-1,3,5,7(1,3)-tetrabenzenacyclooctaphane-12,32,52,72-tetraol；5,11,17,23-tetrakis(2,4,4-trimethylpentan-2-yl)-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-dodecaene-25,26,27,28-tetrol
• CAS: 182496-64-6
• 化学式: C₅₆H₈₀O₄S₄
• 分子量: 945.513
• InChiKey: IVBSXMHLRXMXQL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  20.5
• 重原子数：
  64
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  182
• 氢给体数：
  4
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  p-(1,1,3,3-tetramethylbutyl)thiacalix[4]arene 在 sodium perborate 、 溶剂黄146 作用下， 以 氯仿 为溶剂， 反应 2.0h， 以34.6%的产率得到2,8,14,20-Tetraoxo-5,11,17,23-tetrakis(2,4,4-trimethylpentan-2-yl)-2lambda4,8lambda4,14lambda4,20lambda4-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-dodecaene-25,26,27,28-tetrol
  参考文献：
  名称：

  Selective oxidation of thiacalix[4]arenes to the sulfinyl and sulfonyl counterparts and their complexation abilities toward metal ions as studied by solvent extraction

  摘要：

  Practical methods for the synthesis of sulfinyl-(5,6) and sulfonylcalix[4]arenes (7,8) were provided by the selective oxidation of thiacalix[4]arenes (3,4) with controlled amounts of an oxidant such as NaBO3 or hydrogen peroxide under mild conditions. The coordination ability of thiacalix[4]arene 4 and the sulfinyl and sulfonyl analogs (6,8) toward a wide variety of metal ions was investigated by solvent extraction and compared to that of the conventional methylene-bridged calix[4]arene 2. It was shown that the metal-ion selectivities of the sulfur-containing ligands 4, 6, and 8 were controlled by the oxidation state of the bridging sulfur moiety, which was best understood based on the hard and soft acid-base (HSAB) principle by assuming the critical role of the bridging groups in coordination to the metal center. Thus, 4 preferred soft metal ions by binding with S, while 8 did hard ones by ligating with sulfonyl O in addition to the adjacent two phenoxide oxygens, respectively. In good accordance with this hypothesis, 6 could bind to both hard and soft metal ions by using sulfinyl O and S, respectively. These made sharp contrast to the parent methylene-bridged 2, which could not essentially extract any metal ions at all, lacking lone pair electrons on the methylene bridge for coordination. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)00482-3
• 作为产物：
  描述：

  对特辛基苯酚 在 1,2,3,4,5,6,7,8-八硫杂环辛烷 、 sodium hydroxide 作用下， 以 三甘醇二甲醚 为溶剂， 以14%的产率得到p-(1,1,3,3-tetramethylbutyl)thiacalix[4]arene
  参考文献：
  名称：

  Synthesis of p-tert-Butylthiacalix[4]arene and its Inclusion Property

  摘要：

  A practical method for the synthesis of p-tert-butylthiacalix[4]arene (TC4A), in which the methylene bridges of p-tert-butyl-calix[4]arene (C4A) are replaced by epithio groups, is presented by heating a mixture of p-tert-butylphenol, elemental sulfur S-8, and NaOH as a base catalyst in tetraethylene glycol dimethyl ether. The inclusion behavior of TC4A for a wide range of solvent molecules is examined by recrystallization, showing preference for the guests depending upon the size and/or the substituent of the guests. The X-ray structure of a 1:2 host-guest complex of TC4A with 1,2-dichloroethane reveals that one guest molecule is included in the cavity of TC4A, while the other is included in the crystal lattice to form a clathrate-type complex. It is shown that the inclusion in the cavity is attained by a cooperative deformation of both the host and the guest. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00030-2

文献信息

• Selective oxidation of thiacalix[4]arenes to the sulfinyl- and sulfonylcalix[4]arenes and their coordination ability to metal ions
  作者：Nobuhiko Iki、Hitoshi Kumagai、Naoya Morohashi、Kohki Ejima、Mitsuharu Hasegawa、Setsuko Miyanari、Sotaro Miyano

  DOI：10.1016/s0040-4039(98)01645-1

  日期：1998.10

  Thiacalix[4]arenes in which the four methylene bridges of calix[4]arenes are replaced by sulfide linkages, were selectively oxidized to sulfinyl- or sulfonylcalix[4]arene under mild conditions with control of the stoichiometry of the oxidant. Solvent extraction of the transition and alkaline earth metal ions with these hosts showed that the metal binding ability was governed by the oxidation state of the sulfur functionalities. (C) 1998 Elsevier Science Ltd: All rights reserved.
• Synthesis of p-tert-Butylthiacalix[4]arene and its Inclusion Property
  作者：Nobuhiko Iki、Chizuko Kabuto、Takanori Fukushima、Hitoshi Kumagai、Haruhiko Takeya、Setsuko Miyanari、Tsutomu Miyashi、Sotaro Miyano

  DOI：10.1016/s0040-4020(00)00030-2

  日期：2000.3

  A practical method for the synthesis of p-tert-butylthiacalix[4]arene (TC4A), in which the methylene bridges of p-tert-butyl-calix[4]arene (C4A) are replaced by epithio groups, is presented by heating a mixture of p-tert-butylphenol, elemental sulfur S-8, and NaOH as a base catalyst in tetraethylene glycol dimethyl ether. The inclusion behavior of TC4A for a wide range of solvent molecules is examined by recrystallization, showing preference for the guests depending upon the size and/or the substituent of the guests. The X-ray structure of a 1:2 host-guest complex of TC4A with 1,2-dichloroethane reveals that one guest molecule is included in the cavity of TC4A, while the other is included in the crystal lattice to form a clathrate-type complex. It is shown that the inclusion in the cavity is attained by a cooperative deformation of both the host and the guest. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Selective oxidation of thiacalix[4]arenes to the sulfinyl and sulfonyl counterparts and their complexation abilities toward metal ions as studied by solvent extraction
  作者：Naoya Morohashi、Nobuhiko Iki、Atsushi Sugawara、Sotaro Miyano

  DOI：10.1016/s0040-4020(01)00482-3

  日期：2001.6

  Practical methods for the synthesis of sulfinyl-(5,6) and sulfonylcalix[4]arenes (7,8) were provided by the selective oxidation of thiacalix[4]arenes (3,4) with controlled amounts of an oxidant such as NaBO3 or hydrogen peroxide under mild conditions. The coordination ability of thiacalix[4]arene 4 and the sulfinyl and sulfonyl analogs (6,8) toward a wide variety of metal ions was investigated by solvent extraction and compared to that of the conventional methylene-bridged calix[4]arene 2. It was shown that the metal-ion selectivities of the sulfur-containing ligands 4, 6, and 8 were controlled by the oxidation state of the bridging sulfur moiety, which was best understood based on the hard and soft acid-base (HSAB) principle by assuming the critical role of the bridging groups in coordination to the metal center. Thus, 4 preferred soft metal ions by binding with S, while 8 did hard ones by ligating with sulfonyl O in addition to the adjacent two phenoxide oxygens, respectively. In good accordance with this hypothesis, 6 could bind to both hard and soft metal ions by using sulfinyl O and S, respectively. These made sharp contrast to the parent methylene-bridged 2, which could not essentially extract any metal ions at all, lacking lone pair electrons on the methylene bridge for coordination. (C) 2001 Elsevier Science Ltd. All rights reserved.