A tripod ligand, 1,1,1 tri [1′ (2′ oxa 5′ oxo 6′ aza 6′ bisphenyl)hexyl] propane(L), and its complexes with Ln(NO 3) 3 · n H 2O(where Ln=La, Ce, Pr, Nd) have been synthesized. These new complexes with the ge...A tripod ligand, 1,1,1 tri [1′ (2′ oxa 5′ oxo 6′ aza 6′ bisphenyl)hexyl] propane(L), and its complexes with Ln(NO 3) 3 · n H 2O(where Ln=La, Ce, Pr, Nd) have been synthesized. These new complexes with the general formula of Ln 2L(NO 3) 6· n H 2O(where Ln=La, n =4; Ln=Pr, n =2; Ln=Ce, Nd, n =1) were characterized by elemental analysis, IR spectra, thermal analysis, 1H NMR spectra and molar conductivity. All the complexes are stable in air and their conductances in acetonitrile solution lie in the 149—158 S·cm 2·mol -1 range, indicating that they are 1∶1 type electrolytes. The IR and 1H NMR spectra of the ligand and its complexes show that all the ether oxygen atoms and the CO groups take part in coordination to the metal ions, and the larger shift for ν CO in the IR spectra of the complexes suggests that the Ln—O(carbonyl) bond is stronger than the Ln—O(ether) one which also was inferred from the 1H NMR spectral data . The thermal behaviour of the complexes are similar. The first loss occurs at 85—100.9 ℃ corresponding to the loss of all the water molecules. The weight losses found in this process compare favourably with the theoretical values. Moreover, the relatively low temperatures of dehydration are consistent with the presence of crystal water.展开更多
在催化剂过氧磷钨酸十二烷基吡啶盐(Cat-PW4)的作用下,α-蒎烯与H2O2反应生成主要产物(3R,4R)-4,7,7-三甲基-6-氧杂二环[3.2.1]辛烷-3,4-二醇。不同反应条件对反应转化率和选择性的实验结果表明,最佳反应条件为:12.8 mmolα-蒎烯、5 m ...在催化剂过氧磷钨酸十二烷基吡啶盐(Cat-PW4)的作用下,α-蒎烯与H2O2反应生成主要产物(3R,4R)-4,7,7-三甲基-6-氧杂二环[3.2.1]辛烷-3,4-二醇。不同反应条件对反应转化率和选择性的实验结果表明,最佳反应条件为:12.8 mmolα-蒎烯、5 m L溶剂三氯甲烷、0.2 g催化剂、3.3 m L 30%H2O2,反应温度40℃,反应时间3 h,α-蒎烯转化率和产物的选择性分别为94.7%和39.8%。反应结束后,该产物存在于水相和有机相中,通过萃取和重结晶分离提纯,得率11%,纯度达到98%;其分子结构通过红外光谱、紫外光谱、1H核磁共振谱、13C核磁共振谱、低分辨率质谱及高分辨率质谱确证。展开更多
2-氟-5-[(4-氧代-3,4-二氢二氮杂萘-1-基)甲基]苯甲酸是合成奥拉帕尼的关键中间体。以邻羧基苯甲醛为原料,与亚磷酸二甲酯反应得到磷叶立德,再与2-氟-5-甲酰基苯甲酸进行WittigHorner反应、环合反应得到目标化合物,并对各步反应条件进...2-氟-5-[(4-氧代-3,4-二氢二氮杂萘-1-基)甲基]苯甲酸是合成奥拉帕尼的关键中间体。以邻羧基苯甲醛为原料,与亚磷酸二甲酯反应得到磷叶立德,再与2-氟-5-甲酰基苯甲酸进行WittigHorner反应、环合反应得到目标化合物,并对各步反应条件进行了优化,三步反应总收率70.9%。目标化合物经(1 H NMR)和(MS)确证结构。展开更多
文摘A tripod ligand, 1,1,1 tri [1′ (2′ oxa 5′ oxo 6′ aza 6′ bisphenyl)hexyl] propane(L), and its complexes with Ln(NO 3) 3 · n H 2O(where Ln=La, Ce, Pr, Nd) have been synthesized. These new complexes with the general formula of Ln 2L(NO 3) 6· n H 2O(where Ln=La, n =4; Ln=Pr, n =2; Ln=Ce, Nd, n =1) were characterized by elemental analysis, IR spectra, thermal analysis, 1H NMR spectra and molar conductivity. All the complexes are stable in air and their conductances in acetonitrile solution lie in the 149—158 S·cm 2·mol -1 range, indicating that they are 1∶1 type electrolytes. The IR and 1H NMR spectra of the ligand and its complexes show that all the ether oxygen atoms and the CO groups take part in coordination to the metal ions, and the larger shift for ν CO in the IR spectra of the complexes suggests that the Ln—O(carbonyl) bond is stronger than the Ln—O(ether) one which also was inferred from the 1H NMR spectral data . The thermal behaviour of the complexes are similar. The first loss occurs at 85—100.9 ℃ corresponding to the loss of all the water molecules. The weight losses found in this process compare favourably with the theoretical values. Moreover, the relatively low temperatures of dehydration are consistent with the presence of crystal water.
文摘在催化剂过氧磷钨酸十二烷基吡啶盐(Cat-PW4)的作用下,α-蒎烯与H2O2反应生成主要产物(3R,4R)-4,7,7-三甲基-6-氧杂二环[3.2.1]辛烷-3,4-二醇。不同反应条件对反应转化率和选择性的实验结果表明,最佳反应条件为:12.8 mmolα-蒎烯、5 m L溶剂三氯甲烷、0.2 g催化剂、3.3 m L 30%H2O2,反应温度40℃,反应时间3 h,α-蒎烯转化率和产物的选择性分别为94.7%和39.8%。反应结束后,该产物存在于水相和有机相中,通过萃取和重结晶分离提纯,得率11%,纯度达到98%;其分子结构通过红外光谱、紫外光谱、1H核磁共振谱、13C核磁共振谱、低分辨率质谱及高分辨率质谱确证。
文摘2-氟-5-[(4-氧代-3,4-二氢二氮杂萘-1-基)甲基]苯甲酸是合成奥拉帕尼的关键中间体。以邻羧基苯甲醛为原料,与亚磷酸二甲酯反应得到磷叶立德,再与2-氟-5-甲酰基苯甲酸进行WittigHorner反应、环合反应得到目标化合物,并对各步反应条件进行了优化,三步反应总收率70.9%。目标化合物经(1 H NMR)和(MS)确证结构。
