2,5,8,11,14,20,23,26,29,32-Decaoxatricyclo[31.3.1.115,19]octatriaconta-1(37),15(38),16,18,33,35-hexaene-17,35-dicarboxylic acid | 137738-71-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,5,8,11,14,20,23,26,29,32-Decaoxatricyclo[31.3.1.115,19]octatriaconta-1(37),15(38),16,18,33,35-hexaene-17,35-dicarboxylic acid
• CAS: 137738-71-7
• 化学式: C₃₀H₄₀O₁₄
• 分子量: 624.639
• InChiKey: ATFORLAVFARIDO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  44
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  167
• 氢给体数：
  2
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  2,5,8,11,14,20,23,26,29,32-Decaoxatricyclo[31.3.1.115,19]octatriaconta-1(37),15(38),16,18,33,35-hexaene-17,35-dicarboxylic acid 在 氯化亚砜 作用下， 反应 5.0h， 生成 1,4,7,10,13,20,23,26,29,32-decaoxa<13.13>m-cyclophane-16,35-dicarbonyl chloride
  参考文献：
  名称：

  Synthesis and Properties of Cholesteryl Esters Bearing 32- and 16-Membered Crown Ethers

  摘要：

  The cholesteryl esters (3b and 3a) of 5-carboxy-1,3-phenylene-16-crown-5 and 5-carboxy-4,6-dichloro-1,3-phenylene-16-crown-5 show cholesteric liquid crystalline behavior but only upon heating samples that were rapidly cooled from the isotropic melt in the case of 3a and a monotropic phase for 3b. The dichloro compound 3a was formed by treatment of the corresponding acid 2 with SOCl2 first and then cholesterol; it is believed that the SOCl2 was contaminated with SO2Cl2, leading to the chlorination of the aromatic ring. The dichloro compound 3a was structurally characterized using single crystal X-ray diffraction. 3a crystallizes in the orthorhombic space group P2(1)2(1)2(1) With unit cell parameters of a = 12.76(4) Angstrom, b = 17.511(5) Angstrom, and c = 18.213 Angstrom. Use of freshly opened SOCl2 produced 3b. The reaction of the acid 2 and cholesterol in the presence of dicyclohexylcarbodiimide yielded the acylisourea 4 as the major product (64%) along with 3b (36%) upon treatment with cholesterol. The dicholesteryl ester 9 of bis(5-carboxy-1,3-phenylene)-32-crown-10 (8a) was also synthesized, and by differential scanning calorimetry (DSC) and polarized optical microscopy no liquid crystalline behavior was observed with this system. Apparently the presence of the semirigid crown in the molecule prevents the two cholesteryl moieties from organizing in independent helices. The complexation ability of this cholesteryl crown (9) with methyl viologen bis(hexafluorophosphate) ([paraquat]. 2[PF6]) (12) in acetone has been examined by H-1 NMR spectroscopy; it showed weaker binding than its simple dimethyl ester analog 8b.

  DOI：

  10.1021/jo950097l
• 作为产物：
  描述：

  3,5-二羟基苯甲酸甲酯 在 sodium hydroxide 、 四丁基碘化铵 、 sodium hydride 、 potassium carbonate 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 171.0h， 生成 2,5,8,11,14,20,23,26,29,32-Decaoxatricyclo[31.3.1.115,19]octatriaconta-1(37),15(38),16,18,33,35-hexaene-17,35-dicarboxylic acid
  参考文献：
  名称：

  Difunctional derivatives of bis(m-phenylene)-32-crown-10

  摘要：

  对甲基3,5-二羟基苯甲酸酯（1）与四（乙二醇）二氯化物（3）的缩合优化研究导致1+1环化产物5-羰基甲氧基-m-苯二酚-16-冠-5（5）的产率提高至67%（HPLC），但所需的2+2产物双(5-羰基甲氧基-m-苯二酚)-32-冠-10（4）的产率未提高（28%，HPLC）。然而，在优化后，一个两步程序提供了4的改进产率，并且这个程序被推广用于制备其他双官能单体。用3和取代的间苯二酚的缩合以及随后的转化产生了取代的（R）3,5-双（11-氯-3,6,9-三氧杂十一烷氧基）苯（7, 9-14）。二卤代物7（R = COOCH3），13（R = CHO）和12（R = CH2OSi（Me）2-t-Bu）与甲基3,5-二羟基苯甲酸酯（1）反应产生双（5-羰基甲氧基-m-苯二酚）-32-冠-10（4）（43%），5-羰基甲氧基-m-苯二酚-5'-甲醛-m'-苯二酚-32-冠-10（15）（32%），以及内酯（16a）（18%，源自最初形成的5-羟甲基-m-苯二酚-5'-羰基甲氧基-m'-苯二酚-32-冠-10（16））。随后的反应产生了相应的二酸（17），双（羟甲基）（19），双（溴甲基）（20），二乙酰（18），二甲酰（21），双（对硝基苯氧甲基）（22）和双（乙酰氧甲基）（23）衍生物。关键词：环化，官能化双（m-苯基）冠醚。

  DOI：

  10.1139/v97-165

文献信息

• Synthesis of a water-soluble bis(m-phenylene)-32-crown-10-based cryptand and its pH-responsive binding to a paraquat derivative
  作者：Xiaofan Ji、Mingming Zhang、Xuzhou Yan、Jinying Li、Feihe Huang

  DOI：10.1039/c2cc38472h

  日期：——

  By introducing a third arm with two anionic carboxylate groups, a water-soluble bis(m-phenylene)-32-crown-10-based cryptand was synthesized. Its pH-controlled host-guest complexation with a paraquat derivative in water was studied.

  通过引入具有两个阴离子羧酸盐基团的第三臂，合成了水溶性的双（间亚苯基）-32-冠-10基隐窝分子。研究了其在水中与百草枯衍生物的pH值控制的主客体络合。
• Gunter, Maxwell J.; Johnston, Martin R., Journal of the Chemical Society. Perkin transactions I, 1994, # 8, p. 995 - 1008
  作者：Gunter, Maxwell J.、Johnston, Martin R.

  DOI：——

  日期：——
• A porphyrin-based crown ether co-receptor for the complexation of paraquat
  作者：Maxwell J. Gunter、Martin R. Johnston

  DOI：10.1016/s0040-4039(00)97738-4

  日期：1990.1
• Synthesis and Properties of Cholesteryl Esters Bearing 32- and 16-Membered Crown Ethers
  作者：Devdatt S. Nagvekar、Yadollah Delaviz、Abaneshwar Prasad、Joseph S. Merola、Herve Marand、Harry W. Gibson

  DOI：10.1021/jo950097l

  日期：1996.1.1

  The cholesteryl esters (3b and 3a) of 5-carboxy-1,3-phenylene-16-crown-5 and 5-carboxy-4,6-dichloro-1,3-phenylene-16-crown-5 show cholesteric liquid crystalline behavior but only upon heating samples that were rapidly cooled from the isotropic melt in the case of 3a and a monotropic phase for 3b. The dichloro compound 3a was formed by treatment of the corresponding acid 2 with SOCl2 first and then cholesterol; it is believed that the SOCl2 was contaminated with SO2Cl2, leading to the chlorination of the aromatic ring. The dichloro compound 3a was structurally characterized using single crystal X-ray diffraction. 3a crystallizes in the orthorhombic space group P2(1)2(1)2(1) With unit cell parameters of a = 12.76(4) Angstrom, b = 17.511(5) Angstrom, and c = 18.213 Angstrom. Use of freshly opened SOCl2 produced 3b. The reaction of the acid 2 and cholesterol in the presence of dicyclohexylcarbodiimide yielded the acylisourea 4 as the major product (64%) along with 3b (36%) upon treatment with cholesterol. The dicholesteryl ester 9 of bis(5-carboxy-1,3-phenylene)-32-crown-10 (8a) was also synthesized, and by differential scanning calorimetry (DSC) and polarized optical microscopy no liquid crystalline behavior was observed with this system. Apparently the presence of the semirigid crown in the molecule prevents the two cholesteryl moieties from organizing in independent helices. The complexation ability of this cholesteryl crown (9) with methyl viologen bis(hexafluorophosphate) ([paraquat]. 2[PF6]) (12) in acetone has been examined by H-1 NMR spectroscopy; it showed weaker binding than its simple dimethyl ester analog 8b.
• Difunctional derivatives of bis(<i>m</i>-phenylene)-32-crown-10
  作者：Harry W. Gibson、Devdatt S. Nagvekar

  DOI：10.1139/v97-165

  日期：1997.10.1

  Optimization studies of the condensation of methyl 3,5-dihydroxybenzoate (1) with tetra(ethylene glycol) dichloride (3) resulted in improvement of the yield of the 1 + 1 cyclization product, 5-carbomethoxy-m-phenylene-16-crown-5 (5), to 67% (HPLC), but no improvement in the yield (28%, HPLC) of the desired 2 + 2 product, bis(5-carbomethoxy-m-phenylene)-32-crown-10 (4). However, after optimization, a two-step procedure provided improved yields of 4 and this procedure was generalized to afford other difunctional monomers. Condensation of substituted resorcinols with 3 and subsequent transformations yielded substituted (R) 3,5-bis(11-chloro-3,6,9-trioxaundecyl-oxy)benzenes (7, 9–14). Reaction of dihalides 7 (R = COOCH₃), 13 (R = CHO), and 12 (R = CH₂OSi(Me)₂-t-Bu) with methyl 3,5-dihydroxybenzoate (1) produced bis(5-carbomethoxy-m-phenylene)-32-crown-10 (4) (43%), 5-carbomethoxy-m-phenylene-5′-formyl-m′-phenylene-32-crown-10 (15) (32%), and the lactone (16a) (18%, derived from the initially formed 5-hydroxymethyl-m-phenylene-5′-carbomethoxy-m′-phenylene-32-crown-10 (16)), respectively. Subsequent reactions gave the corresponding diacid (17), bis(hydroxymethyl) (19), bis(bromomethyl) (20), diacetyl (18), diformyl (21), bis(p-nitrophenoxymethyl) (22), and di(acetoxymethyl) (23) derivatives. Keywords: cyclization, functionalized bis(m-phenylene) crown ethers.

  对甲基3,5-二羟基苯甲酸酯（1）与四（乙二醇）二氯化物（3）的缩合优化研究导致1+1环化产物5-羰基甲氧基-m-苯二酚-16-冠-5（5）的产率提高至67%（HPLC），但所需的2+2产物双(5-羰基甲氧基-m-苯二酚)-32-冠-10（4）的产率未提高（28%，HPLC）。然而，在优化后，一个两步程序提供了4的改进产率，并且这个程序被推广用于制备其他双官能单体。用3和取代的间苯二酚的缩合以及随后的转化产生了取代的（R）3,5-双（11-氯-3,6,9-三氧杂十一烷氧基）苯（7, 9-14）。二卤代物7（R = COOCH3），13（R = CHO）和12（R = CH2OSi（Me）2-t-Bu）与甲基3,5-二羟基苯甲酸酯（1）反应产生双（5-羰基甲氧基-m-苯二酚）-32-冠-10（4）（43%），5-羰基甲氧基-m-苯二酚-5'-甲醛-m'-苯二酚-32-冠-10（15）（32%），以及内酯（16a）（18%，源自最初形成的5-羟甲基-m-苯二酚-5'-羰基甲氧基-m'-苯二酚-32-冠-10（16））。随后的反应产生了相应的二酸（17），双（羟甲基）（19），双（溴甲基）（20），二乙酰（18），二甲酰（21），双（对硝基苯氧甲基）（22）和双（乙酰氧甲基）（23）衍生物。关键词：环化，官能化双（m-苯基）冠醚。