Synthesis Of Functional Calixarenes And Their Applications In Catalytic Synthesis Of (Z)-bis-chalcogenide (Se, S) Alkenes

Calixarenes are the third generation of supramolecular compounds after crownethers and cyclodextrins. The latest research shows that calixarenes with moderatecavity shows strong complexing ability to the Cs+cation. However, the recycle ofcalixarenes by dissociating the complexes formed by the Cs+cation and calixarens is achallenge still.The recognition complexation of the Cs+cation and calixarens attributes to theelectrostatic interaction of the positively charged Cs+cation and the rich electronicaromatic rings and ether oxygen atoms. Base on this principle, a new class ofcalixarenes containing quinolinyl in the lower rims was designed and synthesized.The complexations formed by this class calixarenes and the Cs+cation could bereleased to Cs+and calixarenes after the complex is acidified. The major work of thispaper is the synthesis of this new class of calixarenes and their application in catalyticsynthesis of bis-chalcogenide (Se, S) alkenes.The p-tert-butylcalix[4]arenes and p-tert-butylcalix[6]arenes were synthetizedby a “one step reaction” of p-tert-butylphenol and formaldehyde in good yields. The1,3-dialkoxycalix[4]arenes and1,4-dialkoxycalix[6]arenes were synthesized by ReverseFriedel-Crafts Reaction and nucleophilic substitution. The calixarenes containingquinolinyl in the lower rims were synthesized by sulfonation reaction andnucleophilic substitution.The activation of sodium hydroxide, potassium hydroxide, rubidium hydroxideand cesium hydroxide activated by the new class of calixarenes was investigated inthe reaction of terminal alkynes and diaryl disulfides (diaryl selenides). Resultsshowed that good yields were obtained by using potassium hydroxide, rubidiumhydroxide and cesium hydroxide as catalyst. Potassium hydroxide was used becauseof its cheap price and easy got. Bis-sulfide alkenes and bis-selenide alkenes wereobtained in the yields of85%~97%and87%~96%respectively by the reactions ofterminal alkynes and diaryl disulfides (diaryl selenides) in the presence of10mol%calixarenes and20mol%of potassium hydroxide at50℃under nitrogen atmospherein THF for4hours. An efficient and inexpensive route to bis-chalcogenide (Se, S)alkenes was developed. Some important intermediate compounds and all target compounds werecharacterized and confirmed by1HNMR、13CNMR spectras and mass spectra.