Ritter Helmut, Tabatabai Monir, Herrmann Markus
Institute of Organic Chemistry and Macromolecular Chemistry, Heinrich-Heine-University Duesseldorf, Universitaetsstraße 1, D-40225 Duesseldorf, Germany.
Beilstein J Org Chem. 2016 Feb 10;12:245-52. doi: 10.3762/bjoc.12.26. eCollection 2016.
We describe the synthesis of bromo-tert-butyloxycarbonyl (Br-t-BOC)-amino-protected monomers 2-((1-bromo-2-methylpropan-2-yl)oxycarbonylamino)ethyl (meth)acrylate 3a,b. For this purpose, 2-isocyanatoethyl (meth)acrylate 1a,b was reacted with 1-bromo-2-methylpropan-2-ol (2a). The free radical polymerization of (Br-t-BOC)-aminoethyl (meth)acrylates 3a,b yielded poly((Br-t-BOC)-aminoethyl (meth)acrylate) 6a,b bearing protected amino side groups. The subsequent solvolysis of the Br-t-BOC function led to the new polymers poly(2-aminoethyl (meth)acrylate) 8a,b with protonated free amino groups. The monomers and the resulting polymers were thoroughly characterized by (1)H NMR, IR, GPC and DSC methods. The kinetics of the deprotection step was followed by (1)H NMR spectroscopy. The solvent polarity and neighboring group effects on the kinetics of deprotection are discussed.
我们描述了溴代叔丁氧羰基（Br-t-BOC）氨基保护的单体甲基丙烯酸2-((1-溴-2-甲基丙-2-基)氧羰基氨基)乙酯3a、b的合成。为此，甲基丙烯酸2-异氰酸乙酯1a、b与1-溴-2-甲基丙-2-醇（2a）反应。甲基丙烯酸（Br-t-BOC）氨基乙酯3a、b的自由基聚合产生了带有保护氨基侧基的聚甲基丙烯酸（Br-t-BOC）氨基乙酯6a、b。随后Br-t-BOC官能团的溶剂解导致了具有质子化游离氨基的新型聚合物聚甲基丙烯酸2-氨基乙酯8a、b。通过¹H NMR、IR、GPC和DSC方法对单体和所得聚合物进行了全面表征。通过¹H NMR光谱跟踪脱保护步骤的动力学。讨论了溶剂极性和邻基效应对脱保护动力学的影响。
