The methanolysis of poly(triphenylmethyl methacrylate) (PTrMA) and its copolymers P(TrMA-co-MMA), P(TrMA-b-MMA) has been studied in the presence of anhydrous methanol at 40 degrees C by electroconductometric method. I...The methanolysis of poly(triphenylmethyl methacrylate) (PTrMA) and its copolymers P(TrMA-co-MMA), P(TrMA-b-MMA) has been studied in the presence of anhydrous methanol at 40 degrees C by electroconductometric method. It has been found that the methanolysis stability can be obviously improved for the copolymer, especially, the radom copolymer, P(TrMA-co-MMA).展开更多
The copolymerization process of triphenylmethyl methacrylate (TrMA) and methylmethacrylate (MMA) using chiral anionic complex initiator (-) SP-FlLi (Scheme 1) has beenstudied in toluene and THF, respectively. The copo...The copolymerization process of triphenylmethyl methacrylate (TrMA) and methylmethacrylate (MMA) using chiral anionic complex initiator (-) SP-FlLi (Scheme 1) has beenstudied in toluene and THF, respectively. The copolymer obtained in toluene possessed muchhigher specific rotation than that in THF. These copolymers have shown a tendency to a random and a like alternating structure, respectively.展开更多
Optically active poly (triphenylmethyl methacrylate) (PTrMA) with a helical conformation of one-handed screw sense could be formed in an anionic asymmetric polymerization in the presence of (-)-sparteine (Sp). Vogt ha...Optically active poly (triphenylmethyl methacrylate) (PTrMA) with a helical conformation of one-handed screw sense could be formed in an anionic asymmetric polymerization in the presence of (-)-sparteine (Sp). Vogt has proved that the absolute configuration of asymmetric centres in the main chain of a right-handed helical PTrMA was all in S configurations according to the polymerization of展开更多
以烯丙基溴为原料,在N2保护下,乙醚中与镁反应30 m in制得烯丙基溴化镁的乙醚溶液(Ⅰ)。过滤后,将Ⅰ从45℃逐步加热到65℃,蒸出乙醚。然后快速加入四氢呋喃(THF),65℃搅拌20 m in,制得烯丙基溴化镁的THF溶液(Ⅱ)。在冰浴中向Ⅱ缓慢滴加...以烯丙基溴为原料,在N2保护下,乙醚中与镁反应30 m in制得烯丙基溴化镁的乙醚溶液(Ⅰ)。过滤后,将Ⅰ从45℃逐步加热到65℃,蒸出乙醚。然后快速加入四氢呋喃(THF),65℃搅拌20 m in,制得烯丙基溴化镁的THF溶液(Ⅱ)。在冰浴中向Ⅱ缓慢滴加氯代三苯甲烷的THF溶液,搅拌3 h,制得4,4,4-三苯基-1-丁烯(Ⅲ),收率93%。用红外光谱、核磁共振氢谱和碳谱对产物进行了表征。展开更多
Molecular interactions are the key to understanding the structure and properties of materials. Also, it is critical of chiral recognition. Since the molecular interactions at play in chiral discrimination is difficult...Molecular interactions are the key to understanding the structure and properties of materials. Also, it is critical of chiral recognition. Since the molecular interactions at play in chiral discrimination is difficult to investigate under traditional experiment conditions. We have undertaken a computer experiment of van der Waals interaction between chiral molecules and a polymer, which works for chiral separation. Building molecular models, choosing proper force field and Monte Carlo method, we have calculated the difference of interaction energy between isotactic poly (triphenylmethyl methacrylate) and (+) hexahelicene or (-) hexahelicene. It is finally found about 1.379 4 kJ/mol between the polymer and the two chiral hexahelicenes. Reasonably, this difference is regardd as the main reason which induced chiral separation. Furthermore, we compared the results from computer smulation with that from experiment. It can be seen that some details during chiral separation process, such as trailing effect, can also be predicted, and be consistent with the experiment results. Finally, the effective structureal characteristics of the recognition site are pointed out.展开更多
文摘The methanolysis of poly(triphenylmethyl methacrylate) (PTrMA) and its copolymers P(TrMA-co-MMA), P(TrMA-b-MMA) has been studied in the presence of anhydrous methanol at 40 degrees C by electroconductometric method. It has been found that the methanolysis stability can be obviously improved for the copolymer, especially, the radom copolymer, P(TrMA-co-MMA).
文摘The copolymerization process of triphenylmethyl methacrylate (TrMA) and methylmethacrylate (MMA) using chiral anionic complex initiator (-) SP-FlLi (Scheme 1) has beenstudied in toluene and THF, respectively. The copolymer obtained in toluene possessed muchhigher specific rotation than that in THF. These copolymers have shown a tendency to a random and a like alternating structure, respectively.
文摘Optically active poly (triphenylmethyl methacrylate) (PTrMA) with a helical conformation of one-handed screw sense could be formed in an anionic asymmetric polymerization in the presence of (-)-sparteine (Sp). Vogt has proved that the absolute configuration of asymmetric centres in the main chain of a right-handed helical PTrMA was all in S configurations according to the polymerization of
文摘1-Triphenylmethyl 4 imidazolecarboxaldehyde was synthesized from fructose by ring closure, oxidation and N alkylation with an overall yield of 36.5%.
文摘以烯丙基溴为原料,在N2保护下,乙醚中与镁反应30 m in制得烯丙基溴化镁的乙醚溶液(Ⅰ)。过滤后,将Ⅰ从45℃逐步加热到65℃,蒸出乙醚。然后快速加入四氢呋喃(THF),65℃搅拌20 m in,制得烯丙基溴化镁的THF溶液(Ⅱ)。在冰浴中向Ⅱ缓慢滴加氯代三苯甲烷的THF溶液,搅拌3 h,制得4,4,4-三苯基-1-丁烯(Ⅲ),收率93%。用红外光谱、核磁共振氢谱和碳谱对产物进行了表征。
文摘Molecular interactions are the key to understanding the structure and properties of materials. Also, it is critical of chiral recognition. Since the molecular interactions at play in chiral discrimination is difficult to investigate under traditional experiment conditions. We have undertaken a computer experiment of van der Waals interaction between chiral molecules and a polymer, which works for chiral separation. Building molecular models, choosing proper force field and Monte Carlo method, we have calculated the difference of interaction energy between isotactic poly (triphenylmethyl methacrylate) and (+) hexahelicene or (-) hexahelicene. It is finally found about 1.379 4 kJ/mol between the polymer and the two chiral hexahelicenes. Reasonably, this difference is regardd as the main reason which induced chiral separation. Furthermore, we compared the results from computer smulation with that from experiment. It can be seen that some details during chiral separation process, such as trailing effect, can also be predicted, and be consistent with the experiment results. Finally, the effective structureal characteristics of the recognition site are pointed out.
