Refluxing calix[4]-1,3-substituted benzaldehyde derivative（4） with glycine hydrazide derivative, we obtained a novel calix[4]arene hydrazone derivative（5） via ＂1＋2＂ condensation in a yield of 78%. In the reacti...Refluxing calix[4]-1,3-substituted benzaldehyde derivative（4） with glycine hydrazide derivative, we obtained a novel calix[4]arene hydrazone derivative（5） via ＂1＋2＂ condensation in a yield of 78%. In the reaction of compound 4 with L-leucine hydrazide derivative at room temperature, lariat calix[4]-1,3-aza-crown（6） with chiral amino acid group as branched chain was synthesized via ＂1＋ 1＂ addition in a yield of 70%. The preliminary extraction experiments suggested that hosting compounds 5 and 6 possessed good complexation abilities for a-amino acids.展开更多
Unprecedented synthesis of chiral (aza)crown ethers of calix[4]arene derivatives bearing a carboxyl amide bridge was described. The synthesis proceeds through condensation of the corresponding dinitriles with opticall...Unprecedented synthesis of chiral (aza)crown ethers of calix[4]arene derivatives bearing a carboxyl amide bridge was described. The synthesis proceeds through condensation of the corresponding dinitriles with optically active 1,2-aminoalcohols,and is catalyzed by the ZnCl2 Lewis acid at elevated temperature in a very efficient one-pot process. The cavity of calix[4](aza)crowns can encapsulate methanol molecules by O-H...π interaction,which has been confirmed by X-ray crystal structures and ESI-MS.展开更多
Calix[4] (aza) crowns containing amide groups 3a—d were synthesized by the reactions of calix[4]arene (la) or p-tert-butylcalix[4]arene (1b) with N, N′-ethylenebis(2-chloroacetamide) (2a) or N, N′- 1,2-ethylenebis ...Calix[4] (aza) crowns containing amide groups 3a—d were synthesized by the reactions of calix[4]arene (la) or p-tert-butylcalix[4]arene (1b) with N, N′-ethylenebis(2-chloroacetamide) (2a) or N, N′- 1,2-ethylenebis (2-chloroacetamide) (2b) by one step procedure in yields of 85—-90%. Calix[4]-(aza) crowns 4a—b could be obtained by the reduction of 3a—b with LiAlH4 in yields of 51 and 67%, respectively. The nitration of 3a or 3c afforded new chromogenic calix[4]arenes 5a bearing two nitrophenol moieties and 5c bearing one nitro-phenol and one quinone moiety, respectively. The ipso-nitration's of 3b and 3d were also studied. Both gave the products containing one nitro phenol and one quinine moiety. Moreover, a very interesting calix[4]arene derivative 5d containing one cyclohexadienone moiety was also separated as the main product when 3d was ipso-nitrated.展开更多
基金Supported by the National Natural Science Foundation of China(No.20402002)Natural Science Foundation of Fujian Province,China(No.2009J01019)
文摘Refluxing calix[4]-1,3-substituted benzaldehyde derivative（4） with glycine hydrazide derivative, we obtained a novel calix[4]arene hydrazone derivative（5） via ＂1＋2＂ condensation in a yield of 78%. In the reaction of compound 4 with L-leucine hydrazide derivative at room temperature, lariat calix[4]-1,3-aza-crown（6） with chiral amino acid group as branched chain was synthesized via ＂1＋ 1＂ addition in a yield of 70%. The preliminary extraction experiments suggested that hosting compounds 5 and 6 possessed good complexation abilities for a-amino acids.
基金Supported by the National Basic Research Program of China (Grant No. 2007CB925103)the National Natural Science Foundation of China (Grant No. 20602017)NCET-07-0425
文摘Unprecedented synthesis of chiral (aza)crown ethers of calix[4]arene derivatives bearing a carboxyl amide bridge was described. The synthesis proceeds through condensation of the corresponding dinitriles with optically active 1,2-aminoalcohols,and is catalyzed by the ZnCl2 Lewis acid at elevated temperature in a very efficient one-pot process. The cavity of calix[4](aza)crowns can encapsulate methanol molecules by O-H...π interaction,which has been confirmed by X-ray crystal structures and ESI-MS.
基金Project (Nos. 29602010, 29772037) supported by the National Natural Science Foundation of China.
文摘Calix[4] (aza) crowns containing amide groups 3a—d were synthesized by the reactions of calix[4]arene (la) or p-tert-butylcalix[4]arene (1b) with N, N′-ethylenebis(2-chloroacetamide) (2a) or N, N′- 1,2-ethylenebis (2-chloroacetamide) (2b) by one step procedure in yields of 85—-90%. Calix[4]-(aza) crowns 4a—b could be obtained by the reduction of 3a—b with LiAlH4 in yields of 51 and 67%, respectively. The nitration of 3a or 3c afforded new chromogenic calix[4]arenes 5a bearing two nitrophenol moieties and 5c bearing one nitro-phenol and one quinone moiety, respectively. The ipso-nitration's of 3b and 3d were also studied. Both gave the products containing one nitro phenol and one quinine moiety. Moreover, a very interesting calix[4]arene derivative 5d containing one cyclohexadienone moiety was also separated as the main product when 3d was ipso-nitrated.
