Concave reagents, 8. Concave pyridines and 1,10‐phenanthrolines with sulfonamide bridgeheads. Increased basicity by 4‐diethylamino substitution of the pyridine unit
Concave reagents, 8. Concave pyridines and 1,10‐phenanthrolines with sulfonamide bridgeheads. Increased basicity by 4‐diethylamino substitution of the pyridine unit
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凹面试剂，8. 凹面吡啶和带有磺酰胺桥头的 1,10-菲咯啉 通过吡啶单元的 4-二乙氨基取代增加碱度。
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发表时间：
1991
期刊：
影响因子：
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通讯作者：
Michael Müller
中科院分区：
文献类型：
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作者：
U. Lüning;R. Baumstark;Michael Müller
以大环吡啶二胺12或1,10-菲罗啉二胺16与烷基二磺酰氯s - 14桥接，合成了双大环凹型吡啶二磺酰胺2和凹型1,10-菲罗啉二磺酰胺4。与凹形吡啶-和1,10-菲罗啉双内酰胺1和3相比，由于没有酰胺构象，新化合物2和4具有更简单的1H-NMR谱和更高的熔点；与1相比，2的碱度降低了约100倍。通过在吡啶环的4位上引入给体取代基，可以很容易地补偿碱度损失。4-二乙胺取代基如预期的那样增加了凹型吡啶1和2的碱度（约+ 4个pK单位）。由于没有发现氨基取代的凹形吡啶1和2与预期的碱度和反应性有偏差，同样在这些位阻吡啶中，吡啶氮原子是碱度和反应性的中心。-描述了新构建块的合成，即4-二乙基氨基-2,6-吡啶二乙醛（9c），聚醚基双（磺酰氯）14b，单大环二胺12e-h与五乙基乙二醇链或4-二乙基取代基。
Bimacrocyclic concave pyridinebissulfonamides 2 and concave 1,10-phenanthrolinebissulfonamides 4 have been synthesized by bridging macrocyclic pyridinediamines 12 or 1,10-phenanthrolinediamines 16 with alkylenebis(sulfonyl chloride)s 14. In contrast to concave pyridine- and 1,10-phenanthrolinebislactams 1 and 3, the new compounds 2 and 4 exhibit simpler 1H-NMR spectra and sharper melting points due to the absence of amide conformers; in comparison to 1, the basicities of 2 are decreased by a factor of ca. 100. By introduction of donor substituents into the 4-position of the pyridine ring the basicity loss can be easily compensated. The 4-diethylamino substituent increases the basicity of the concave pyridines 1 and 2 as expected (ca. + 4 pK units). Since no deviations from the expected basicity and reactivity for the amino-substituted concave pyridines 1 and 2 have been found, also in these sterically hindered pyridines, the pyridine nitrogen atom is the centre of basicity and reactivity. – The synthesis of new building blocks is described, i.e. 4-diethylamino-2,6-pyridinedicarbaldehyde (9c), the polyether-based bis(sulfonyl chloride) 14b, the monomacrocyclic diamines 12e–h with a pentaethyleneglycol chain or a 4-diethylamino substituent.