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通过添加对映体拆分剂,合成了4种含膦手性的丙炔胺磷酸酯单体[HC帒CC H2NH(PO)R1R2].单体1,R1=OPh,R2=NC4H7COOCH3;单体2,R1=OPh,R2=NC4H7COOCH2CH3;单体3,R1=OPh,R2=NC4H7-COOC(CH3)3;单体4,R1=Ph,R2=NC4H7COOC(CH3)3].1H-NMR和31P-NMR表征可知对映体(单体1)不能被拆分剂拆分,而单体2、单体3、单体4通过拆分剂可以制得单一手性的磷化合物.以(nbd)Rh+[η6-C6H5B--(C6H5)3]为催化剂,以三氯甲烷为溶剂成功得到聚合物分子量范围在0.4×10-4～0.7×10-4,分子量分布在1.26～1.98范围的3种含手性膦侧基的丙炔胺类聚合物.比旋光度([α]D)、圆二色谱(CD)对聚合物的不同侧基及温度对光学活性的影响表明,聚合物具有良好的光学活性且能够形成单一方向的螺旋构象,说明膦手性在构建螺旋聚合物具有重要作用.
Four kinds of phosphinylated chiral propargylamine phosphate monomers [HC 帒 CC H2NH (P O) R1R2] were synthesized by adding enantiomer resolving agent. Monomer 1, R1 = OPh and R2 = NC4H7COOCH3. Monomer 2, R1 = OPh, R2 = NC4H7COOCH2CH3; Monomer 3, R1 = OPh, R2 = NC4H7-COOC (CH3) 3; Monomer 4, R1 = Ph, R2 = NC4H7COOC (CH3) 3] .1H-NMR And 31P-NMR characterization shows enantiomer (monomer 1) can not be resolved by the resolving agent, and monomer 2, monomer 3, monomer 4 by resolving agent can be prepared monochiral phosphorus compounds. ( nbd) Rh + [η6-C6H5B - (C6H5) 3] as catalyst, the molecular weight range of the polymer was 0.4 × 10-4 ~ 0.7 × 10-4 and the molecular weight distribution was in the range of 1.26 ~ 1.98 Three kinds of propynyl amine containing chiral phosphine side groups.The influence of specific rotation ([α] D), circular dichroism (CD) on the different side groups of the polymer and temperature on the optical activity showed that the polymer It has a good optical activity and can form a single direction of the helical conformation, indicating that phosphine chirality plays an important role in the construction of helical polymers.