COMPLEXATION OF ARENES BY MACROCYCLIC HOSTS IN AQUEOUS AND ORGANIC SOLUTIONS
COMPLEXATION OF ARENES BY MACROCYCLIC HOSTS IN AQUEOUS AND ORGANIC SOLUTIONS
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DOI：
10.1021/ja00269a025
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发表时间：
1986-04-30
影响因子：
15
通讯作者：
GRIEBEL, D
中科院分区：
文献类型：
--
作者：
DIEDERICH, F;DICK, K;GRIEBEL, D
作为中性芳烃的球形主体，合成了大双环化合物2和3。1-Acetyl-4，4-bis-[4-succinimidyloxycarbonylmethoxy-3，5-dimethylphenyl]piperidine(8)和1-ethyl-4，4-bis[2-aminoethoxy)-3，5-dimethylphenyl]piperidine(10)被环化为四氧二氮[7.1.7.1]对环芳烃4。环化组分8是从1-acetyl-1，4-bis(4-hydroxy-3，5-dimethylphenyl)piperidine出发，按照反应顺序6.fwdarw得到的。7.fwdarw。8.利用反应序列8.fwdarw得到化合物10。9.fwdarw。10.减少4个带来1‘’，1‘’‘’-diethyl-9，13，17，19，29，33，37，39-octamethyldispiro[17，21，27-tetraoxa-4，24-diaza[7.1.7.1]paracyclophane-14，4‘’：34，4‘’‘’-bispiperidine](5)。5与1-benzyloxycarbonyl-1，4-bis[chloroformylmethoxy-3，5-dimethylphenyl]piperidine(12)环化，通过反应序列6.fwdarw得到。11.fwdarw。12，得到大双环化合物13。讨论了N-羟基琥珀酰亚胺酯作为活性羧酸衍生物进行酰胺大环化反应的优点。13通过遵循序列13.fwdarw被转化到靶主机2中。14.fwdarw。2.通过使用序列14.fwdarw获得宿主3。15.fwdarw。3或通过还原宿主2。宿主3，1‘’，1‘’‘’，1‘’‘’‘’-triethyl-6，12，22，28，37，43，48，51，52，55，56，59-dodecamethyltrispiro[4，14，20，30，35，45-hexaoxa-1，17-diazaoctacyclo[15.15.15.25.8.210，13.221.24.226，29.236，39.241，44]nonapentaconta-5，7，10，12，21，23，26，28，36，38，41，43，48，50，52，54，56，58-octadecaene-9，4‘’：25，4‘’‘’：40，4‘’‘’-trispiperidine]，具有D3h对称性。在宿主3中，三个带有N-乙基哌啶环的二苯甲烷单元分别由两个.sbd.O.sbd.CH2.sbd.CH2.sbd连接。链连接到D3h对称轴经过的两个隐氮原子。在宿主2中，三个二苯基甲烷单元中的一个通过两个O.sbd.CH2.sbd.C(O)桥连接到两个氮基上。研究了在弱酸性水溶液中，主体2、3与中性芳烃的络合作用。通过固-液和液-液萃取测定了络合物的缔合常数。用核磁共振氢谱确定了配合物在水溶液中的几何构型。讨论了与两个非常相似的宿主2和3观察到的结合方面的显著差异。首次广泛地研究了中性芳烃与人工大环主体在不同极性的有机溶剂中的结合。用电子吸收和发射光谱和核磁共振氢谱研究了芳烃与主体2、3和16在有机溶剂中的络合反应。在有机溶剂中，主体3比主体2和主体16是更好的芳烃粘结剂。在苯中，甚至观察到了3与茂、芘或荧菲的络合作用。在所有的溶剂中，发现特定的主体和客体的络合物的几何构型非常相似。根据络合物中主客体间吸引范德华相互作用的贡献和溶剂化-解溶过程的贡献，讨论了络合物在有机溶剂中的缔合常数。
As spherical hosts for neutral arenes, the macrobicyclic compounds 2 and 3 were synthesized. 1-Acetyl-4,4-bis-[4-succinimidyloxycarbonylmethoxy-3,5-dimethylphenyl]piperidine (8) and 1-ethyl-4,4-bis[2-aminoethoxy)-3,5-dimethylphenyl]piperidine (10) were cyclized to the tetraoxadiaza[7.1.7.1]paracyclophane 4. Cyclization component 8 was obtained by starting from 1-acetyl-1,4-bis(4-hydroxy-3,5-dimethylphenyl)piperidine and following the reaction sequence 6 .fwdarw. 7 .fwdarw. 8. Compound 10 was obtained with use of the reaction sequence 8 .fwdarw. 9 .fwdarw. 10. Reduction of 4 afforded 1'',1''''-diethyl-9,13,17,19,29,33,37,39-octamethyldispiro[17,21,27-tetraoxa-4,24-diaza[7.1.7.1]paracyclophane-14,4'':34,4''''-bispiperidine] (5). 5 was cyclized with 1-benzyloxycarbonyl-1,4-bis[chloroformylmethoxy-3,5-dimethylphenyl]piperidine (12), obtained by the reaction sequence 6 .fwdarw. 11 .fwdarw. 12, to yield the macrobicyclic compound 13. The advantages of amide macrocyclizations with N-hydroxysuccinimide esters as activated carboxylic acid derivatives are discussed. 13 was tranformed into the target host 2 by following the sequence 13 .fwdarw. 14 .fwdarw. 2. Host 3 was obtained by using the sequence 14 .fwdarw. 15 .fwdarw. 3 or by reduction of host 2. Host 3, 1'',1'''',1''''''-triethyl-6,12,22,28,37,43,48,51,52,55,56,59-dodecamethyltrispiro[4,14,20,30,35,45-hexaoxa-1,17-diazaoctacyclo[15.15.15.25.8.210,13.221.24.226,29.236,39.241,44]nonapentaconta-5,7,10,12,21,23,26,28,36,38,41,43,48,50,52,54,56,58-octadecaene-9,4'':25,4'''':40,4''''-trispiperidine], has D3h symmetry. In host 3, three diphenylmethane units bearing N-ethylpiperidine rings are attached each by two .sbd.O.sbd.CH2.sbd.CH2.sbd. chains to two cryptand-nitrogen atoms, through which the D3h symmetry axis passes. In host 2, one of the three diphenylmethane units is attached to the two nitrogens by two O.sbd.CH2.sbd.C(O) bridges. The complexation between hosts 2 and 3 and neutral arenes in weakly acidic aqueous solution is studied. Association constants of the complexes were determined from solid-liquid and liquid-liquid extractions. The geometry of complexes in aqueous solution was elucidated by 1H NMR spectroscopy. The considerable difference in binding, which was observed with the two very similar hosts 2 and 3, is discussed. The first extensive study of the binding between neutral arenes and artificial macrocyclic hosts in various organic solvents of different polarity is presented. The complexation between arenes and hosts 2, 3, and 16 in organic solvents was monitored by electronic absorption and emission spectroscopy and 1H NMR spectroscopy. Host 3 is a better binder for arenes in organic solvents than hosts 2 and 16. Complexation between 3 and perylene, pyrene, or fluoranthene was even observed in benzene. The geometry of the complex of a specific host and a guest was found to be very similar in all solvents. The association constants of the complexes in organic solvents are discussed in terms of the contribution of attractive van der Waals interaction between host and guest in the complex and in terms of contributions of solvation-desolvation processes.